CN1839112A - Method for producing aromatic carbonate - Google Patents
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- CN1839112A CN1839112A CN 200480024194 CN200480024194A CN1839112A CN 1839112 A CN1839112 A CN 1839112A CN 200480024194 CN200480024194 CN 200480024194 CN 200480024194 A CN200480024194 A CN 200480024194A CN 1839112 A CN1839112 A CN 1839112A
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Abstract
A method for producing an aromatic carbonate, comprising: (1) performing a reaction between an organometal compound and carbon dioxide to obtain a reaction mixture containing a dialkyl carbonate formed by the reaction, (2) separating the dialkyl carbonate from the reaction mixture to obtain a residual liquid, (3) reacting the residual liquid with an alcohol to form at least one organometal compound and form water and removing the water from the organometal compound, and (4) reacting the dialkyl carbonate separated in step (2) with an aromatic hydroxy compound to obtain an aromatic carbonate.
Description
Background of invention
Technical field
The present invention relates to a kind of method of producing aromatic carbonate.More specifically, the present invention relates to a kind of method of producing aromatic carbonate, it comprises: (1) carries out the reaction between organometallic compound and the carbonic acid gas, obtain containing the reaction mixture of the dialkyl carbonate that generates by this reaction, (2) from described reaction mixture, isolate described dialkyl carbonate, obtain residual liquid, and partly or entirely side by side carry out the following step (3) and (4) in any order: (3) make described residual liquid and alcohol reaction, generate at least a organometallic compound, also generate water, from described organometallic compound, remove described water, (4) make the described dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.
The favourable part of the inventive method not only is this method without any need for toxicant with do not produce any corrosives, but also is that the amount of by product intermediate product considerably less and that produce at the production period of required aromatic carbonate can recirculation.Thereby the inventive method is favourable for the consideration of environment protection, can produce highly purified aromatic carbonate simple and efficiently.
Prior art
Aromatic carbonate is widely used as the carbonyl source, for example is used as the raw material of producing polycarbonate, isocyanic ester and medicine, and has needed to develop the method for low cost production aromatic carbonate.
As the method for on technical scale, producing aromatic polycarbonate, can mention following method (i) and (ii):
(i) interfacial polymerization (wherein making phosgene and bis-phenol polymeric method on the interface between methylene dichloride phase and the water in the presence of the suitable chlorine receptor); With
(ii) method of fusion (wherein making diphenyl carbonate and bis-phenol polymeric method) by transesterify/dephenolize reaction.
Aforesaid method (i) (being interfacial polymerization) uses methylene dichloride, and aforesaid method (ii) (being method of fusion) do not use methylene dichloride.Recently, because alkyl halide has caused the water pollution problems, therefore, do not use the method for fusion of methylene dichloride to arouse attention.
As the well-known process of the aromatic carbonate (for example diphenyl carbonate) of producing the raw material that is used as above-mentioned method of fusion, can mention following method 1) to 5):
1) use phosgene to produce the method (for example referring to following patent literature 1) of aromatic carbonate as the carbonyl source;
2) use carbon monoxide to produce the method for aromatic carbonate as the carbonyl source:
3) produce the method for aromatic carbonate by diaryl esters of oxalic acid;
4) use urea (or derivatives thereof) to produce the method for aromatic carbonate as the carbonyl source; With
5) use carbonic acid gas to produce the method for aromatic carbonate as the carbonyl source.
About method 1), give an explaination below.The example of concrete pattern method 1) comprises aqueous solution pattern, wherein introduces phosgene in the aqueous solution of metal phenates; Interface model, wherein the production of aromatic carbonate is carried out in the two-phase system that comprises organic solvent phase and water; And the gas phase pattern, phenol and phosgene are reacted in gas phase.Each of these patterns can easily be produced aromatic carbonate.But, because method 1) adopt the phosgene that has toxicity and high corrosion, so method 1) shortcoming be that the transportation of phosgene and storage need significant care, and the maintenance costliness of production unit, and this maintenance is to guarantee that safety institute is indispensable.In addition, in method 1) in, supervene the hydrochloric acid of a large amount of high corrosion, cause difficult problem on the waste disposal or the like thus.And, because method 1) aromatic carbonate (for example diphenyl carbonate) that obtains contains inevitably as the impurity chlorine-containing compound, so method 1) also cause following serious problems.When a kind of like this aromatic carbonate that contains chlorine-containing compound is used for producing polycarbonate by method of fusion, even the amount of chlorine-containing compound in aromatic carbonate is considerably less, it also can cause being used to producing the inactivation of catalyzer of polycarbonate and the variable color of the polycarbonate produced.In order to remove the chlorine-containing compound that in aromatic carbonate, contains with considerably less amount (weight based on aromatic carbonate is generally several ppm by weight), extra purification step become necessary (for example referring to following patent literature 2).
As seen from the above, method 1) have some serious problems, for example use toxicant as raw material, supervene corrosive compound and in the aromatic carbonate of being produced, contain impurity (for example chlorine-containing compound).
About method 2), give an explaination below.Method 2) is a kind of oxidative carbonylation method, wherein uses carbon monoxide to produce aromatic carbonate (for example diphenyl carbonate) by oxygen and aromatic hydroxy compound as the carbonyl source.In method 2) in the carbon monoxide that uses have toxicity.Therefore, the transportation and the processing of carbon monoxide need significant care, and the maintenance costliness of production unit, and this maintenance is to guarantee that in the production of aromatic carbonate safety institute is indispensable.In addition, method 2) adopt chlorine or chlorine-containing compound as the part of catalyzer or as promotor.Therefore, as the method 1 of above-mentioned use phosgene) situation, by method 2) aromatic carbonate produced contains chlorine-containing compound inevitably as impurity.And, method 2) adopt palladium as catalyzer, however this catalyzer is expensive and be difficult to reclaim.Therefore, method 2) become extremely expensive and complicated method inevitably.
Thereby, method 2) also have some serious problems, for example use corrosive nature that toxic chemical causes as raw material, by chlorine, in the aromatic carbonate of being produced, contain chloride impurity and production cost height.
As to method 2) similar ordinary method, can mention a kind of like this method, wherein obtain methylcarbonate by carbon monoxide, oxygen and methyl alcohol, and make gained methylcarbonate and aromatic hydroxy compound reaction, obtain aromatic carbonate by oxidation carbonylation.But, this method also causes a problem-a large amount of chlorine-containing compounds of use in oxidation carbonylation, consequently contains the production unit (for example referring to following patent literature 3) that the corrosion of chlorine-containing compound or this chlorine-containing compound is used in this method in the methylcarbonate of being produced by oxidation carbonylation.
About method 3), give an explaination below.Method 3) is a kind of like this method, wherein produces diaryl esters of oxalic acid, make the diaryl esters of oxalic acid that is generated carry out de-carbonyl reaction, produce diaryl carbonate (for example diphenyl carbonate) by carbon monoxide as raw material.By method 3) diaryl carbonate produced contains a large amount of impurity, for example from raw material deutero-furanoid and chlorine-containing compound.Therefore, if the not purified production polycarbonate that is directly used in of the diaryl carbonate of being produced, the then polycarbonate of being produced variable color inevitably presents yellow.In order to eliminate this problem, must carry out some extra steps of from diaryl carbonate, removing impurity, so that obtain the diaryl carbonate (for example referring to following patent literature 4) of purifying.
About method 4), give an explaination below.Method 4) is a kind of like this method, wherein makes urea and alcohol reaction, obtain dialkyl carbonate, make the reaction of gained dialkyl carbonate and aromatic hydroxy compound, obtain aromatic carbonate (for example diphenyl carbonate) as carbonate source.When with aforesaid method 1) to 3) when comparing, method 4) the raising part be that the urea as raw material does not have toxicity basically.But,, supervene allophanate inevitably, reduce the selectivity of dialkyl carbonate thus producing the reaction of dialkyl carbonate from urea and alcohol.Therefore, by method 4) produce aromatic carbonate (for example diphenyl carbonate) and become expensive inevitably.And then the alkyl carbamate and the dialkyl carbonate that generate as intermediate product form azeotropic mixture together, so the separation of dialkyl carbonate is very difficult.In order not contained the pure carbon acid dialkyl ester of alkyl carbamate, the additional step that relates to troublesome operations is essential (for example referring to following patent literature 5).In addition, be used to dispose by product, for example the equipment of above-mentioned allophanate also is essential.Therefore, by method 4) produce aromatic carbonate and become complicated inevitably.
About method 5), give an explaination below.Method 5) is a kind of like this method, wherein make as reactions such as the carbonic acid gas in carbonyl source and ethylene oxides, obtain cyclic carbonate, make gained cyclic carbonate and alcohol reaction, obtain dialkyl carbonate, make the reaction of gained dialkyl carbonate and aromatic hydroxy compound, obtain aromatic carbonate (for example referring to patent documentation 6).The favourable part of this method is: using does not have toxicity and cheap carbonic acid gas basically as raw material.But in method 5) in, also produced ethylene glycol with diaryl carbonate (for example diphenyl carbonate), and very difficult by ethylene glycol regenerating oxidation ethene.Therefore, must be from method 5) related above-mentioned reaction produce above-mentioned ethylene oxide separately as raw material.
Thereby, method 5) problem for example be: the production as the ethylene oxide of raw material is essential, and the ethylene glycol that produces with diaryl carbonate can not recirculation in the production of aromatic carbonate.
As with aforesaid method 5) (in the method, make carbonic acid gas and ethylene oxide reaction as the carbonyl source, obtain cyclic carbonate, make gained cyclic carbonate and alcohol reaction, obtain dialkyl carbonate, make the reaction of gained dialkyl carbonate and aromatic hydroxy compound, obtain aromatic carbonate) similar methods, known have a kind of like this method of wherein directly producing dialkyl carbonate by carbonic acid gas and alcohol, and this method does not produce cyclic carbonate intermediate product (referring to following patent literature 7,8 and 9).When the alcohol that uses in this method is when producing as organic dewatering agent with acetal, produce the water consumption that is generated in the reaction of dialkyl carbonate in carbonic acid gas and alcohol reaction and producing in the reaction of alcohol, promote above-mentioned reaction to produce dialkyl carbonate thus.Provide more specifically and explain that reaction related in the aforesaid method is represented in formula (4) and (5) below with reference to following formula (4) and (5) (wherein the Me representative is as methyl of the representative example of alkyl).The water of supervening in the balanced reaction (just producing the reaction of alkyl carbonate) by following formula (4) representative is used for by the balanced reaction of formula (5) representative (just producing the reaction of alcohol).Therefore, the amount of the water of supervening in the reaction of producing alkyl carbonate reduces, and thus, the molecular balance of formula (4) moves to the direction that forms required product.Thereby, can obtain dialkyl carbonate (being methylcarbonate) by carbonic acid gas and alcohol (being methyl alcohol).But, in the method that relates to formula (4) and (5) reaction, therefore moles such as the consumption of acetal supervene acetone (being derived by acetal) with dialkyl carbonate in the dialkyl carbonate of being produced.With the acetone conversion of supervening is that acetal is difficult, because be that the reaction of acetal (organic dewatering agent) is to be difficult to the dehydration reaction of carrying out with acetone conversion.Therefore, must use a large amount of acetals as raw material, and energy efficiency is relatively poor.For this reason, aforesaid method not commercialization as yet.
Even use inorganic dewatering agent to replace organic dewatering agent (for example acetal), also can produce above-mentioned same problem, that is to say, mineral compound as dewatering agent absorbs water, the mineral compound that it needs big energy to make and has absorbed water dewaters, can be used as the mineral compound of dewatering agent with regeneration, the result makes can not be with the low cost production dialkyl carbonate.Therefore, use the also not commercialization as yet of method of inorganic dewatering agent.
As mentioned above, the method that some produce aromatic carbonate has been proposed; But, these methods have variety of issue, for example use toxicant as raw material; Chlorine-containing compound corrosion production unit; Remove the troublesome operations of by product (for example chlorine-containing compound); And by product is difficult to (impossible) and changes into raw material.Even use carbonic acid gas (do not have basically toxicity and not chlorine-containing compound) as the carbonyl source, also existing problems still for example generate by used dewatering agent deutero-by product and by product and need regeneration or dispose dewatering agent.
Thereby, needing a kind of method of producing aromatic carbonate of exploitation, its favourable part is that not only this method does not need to use any toxicant and do not generate any corrosives, but also is that the amount of by product and by product is considerably less.Thereby this method is favourable for the consideration of environment protection, can produce highly purified aromatic carbonate simple and efficiently.
Patent documentation 1: Japanese Patent No.3071008
Patent documentation 2: do not examine the flat 8-198816 of Japanese Patent Application Publication specification sheets No.
Patent documentation 3: do not examine the flat 7-145109 of Japanese Patent Application Publication specification sheets No.
Patent documentation 4: do not examine Japanese Patent Application Publication specification sheets No.2002-47251
Patent documentation 5: do not examine Japanese Patent Application Publication specification sheets No.2000-1461
Patent documentation 6: do not examine the flat 9-40616 of Japanese Patent Application Publication specification sheets No.
Patent documentation 7: do not examine Japanese Patent Application Publication specification sheets No.2001-247519
Patent documentation 8: German Patent No.4310109
Patent documentation 9: do not examine Japanese Patent Application Publication specification sheets No.2001-31629
Summary of the invention
In this case, the inventor has carried out research extensively and profoundly, in the hope of solving the problems referred to above that prior art exists.In its research, the inventor has adopted the technology of formerly inventing WO03/055840 and WO 04/014840, these two pieces of documents relate to the method for continuous production dialkyl carbonate separately, this method comprises reacts organometallic compound, carbonic acid gas and optional alcohol each other, obtain containing the reaction mixture of dialkyl carbonate, from this reaction mixture, isolate dialkyl carbonate, obtain residual liquid, from this residual liquid, regenerate organometallic compound and recirculation institute regenerated organometallic compound.As a result, the inventor has successfully improved above-mentioned invention formerly, has realized the present invention.That is to say, have been found that, prior art with all problems solved by a kind of like this method, this method comprises: (1) carries out the reaction between organometallic compound and the carbonic acid gas, obtain containing the reaction mixture of the dialkyl carbonate that generates by this reaction, (2) from described reaction mixture, isolate described dialkyl carbonate, obtain residual liquid, and partly or entirely side by side carry out the following step (3) and (4) in any order: (3) make described residual liquid and alcohol reaction, generate at least a organometallic compound, also generate water, from described organometallic compound, remove described water, (4) make the described dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.Particularly, the favourable part of the inventive method is that not only this method does not need to use any toxicant and do not produce any corrosives, but also is that the amount of by product intermediate product considerably less and that produce at the production period of required aromatic carbonate can recirculation.Therefore, the inventive method is favourable for the consideration of environment protection, can produce highly purified aromatic carbonate simple and efficiently.The present invention is based on this discovery is accomplished.
More specifically, in the methods of the invention, can recirculation at the intermediate product that production period generated of required aromatic carbonate, and by the aromatic carbonate and the water that only obtain as the carbonic acid gas of raw material and aromatic hydroxy compound as product, wherein beyond removing carbon dioxide and the aromatic hydroxy compound, it is essential not having other raw material basically.Thereby, the inventive method solved prior art with all problems, for example use the toxicant as raw material, chlorine-containing compound corrosion production unit, generation is difficult to isolating by product and intermediate product, produces by product and contain chlorine-containing compound in the aromatic carbonate of being produced.
Therefore, the purpose of this invention is to provide a kind of method of producing aromatic carbonate, the favourable part of this method is that not only this method does not need to use any toxicant and do not produce any corrosives, but also is that the amount of by product is considerably less and can circulates at the intermediate product that the production period of required aromatic carbonate generates.Thereby this method is favourable for the consideration of environment protection, can produce highly purified aromatic carbonate simple and efficiently.
Connection with figures and appended claim book, above and other objects of the present invention, feature and advantage will become apparent from following detailed description.
The accompanying drawing summary
In the accompanying drawings:
Fig. 1 is the schema that shows the embodiment of the inventive method of producing aromatic carbonate;
Fig. 2 is the schema that shows the embodiment of the inventive method of producing diaryl carbonate;
Fig. 3 is the schema that shows the example of related step in the inventive method, that is, the step of the inventive method (3), produce dibutyl tin two alcoholate step, produce the step of dioctyl tin two alcoholate and the step of fractionation by distillation water from alcohol;
Fig. 4 is the schema that shows the specific examples of the inventive method step (2);
Fig. 5 is the schema that shows the specific examples of the inventive method step (4);
Fig. 6 is the schema that shows the specific examples of the inventive method step (5);
Fig. 7 is the schema that shows the specific examples of the pure recirculation step of carrying out in the methods of the invention;
Fig. 8 is the schema that shows the specific examples of the diaryl carbonate purification step that carries out in the methods of the invention;
Fig. 9 is the schema that shows another specific examples of the diaryl carbonate purification step that carries out in the methods of the invention;
Figure 10 is the schema that shows the specific examples of the step of separating alcohol from dialkyl carbonate of carrying out in the methods of the invention;
Figure 11 is the schema that shows the specific examples of the dialkyl carbonate purification step that carries out in the methods of the invention; And
Figure 12 is the schema that shows the specific examples of the dialkyl carbonate recirculation step of carrying out in the methods of the invention.
The explanation of reference number
1: reaction vessel
2,3,4,5,8,10,12,15,17,20,21,24,26,31,33,34,35,37,40,44,46,48,51,55,57,59,62,66,68,70,73,77,79,81,84,88,90,92,95,99,101,103,106,110,112,114,117,121,123,128,132,133,134,136: conduit
6,18,28,41,52,63,74,85,96,107,118: condenser
7,9,16,19,23,29,32,47,58,69,80,91,102,113,124,125,126,127,131,135,137,138,139,140: storage tank
11: the device that removes alcohol
13,38,49,60,71,82,93,104,115: preheater
14,39,50,61,72,83,94,105,116: the continuous multi-stage distillation tower
22,45,56,67,78,89,100,111,122: reboiler
25: the container that removes carbonic acid gas
27: the multistage distillation tower
42,53,64,75,86,97,108,119,129: gas-liquid separation device
30: the thin film distillation device
36,43,54,65,76,87,98,109,120,130: pressure regulator valve
Detailed Description Of The Invention
According to the present invention, a kind of method of producing aromatic carbonate is provided, it comprises:
(1) carry out reaction between organo-metallic compound and the carbon dioxide, obtain containing the reactant mixture of the dialkyl carbonate that is generated by this reaction,
(2) from described reactant mixture, isolate described dialkyl carbonate, obtain residual liquid, and
Side by side carry out in any order or partially or completely the following step (3) and (4):
(3) make described residual liquid and alcohol reaction, generate at least a organometallic compound, also generate water, from described organometallic compound, remove described water,
(4) make isolating described dialkyl carbonate and aromatic hydroxy compound reaction in step (2), obtain aromatic carbonate.
In order to understand the present invention easily, numbering is enumerated essential characteristic of the present invention and various preferred below
Embodiment.
1, a kind of method of producing aromatic carbonate comprises:
(1) carry out reaction between organometallic compound and the carbonic acid gas, obtain containing the reaction mixture of the dialkyl carbonate that generates by this reaction,
(2) from described reaction mixture, isolate described dialkyl carbonate, obtain residual liquid, and
Partly or entirely side by side carry out the following step (3) and (4) in any order:
(3) make described residual liquid and alcohol reaction, generate at least a organometallic compound, also generate water, from described organometallic compound, remove described water and
(4) make the described dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.
2, according to top the 1st method, wherein the described aromatic carbonate that obtains in step (4) is at least a compound that is selected from carbonate alkyl aryl ester and diaryl carbonate.
3,, wherein in step (3), will be recycled to step (1) from the described organometallic compound of wherein removing described water according to top the 1st or 2 method.
4,, wherein in step (4), will be recycled to step (3) with the alcohol that described aromatic carbonate generates according to the top the 1st to 3 any one method.
5, according to the top the 1st to 4 any one method, wherein the dialkyl carbonate that will reclaim in step (4) is recycled to step (4).
6, according to the top the 1st to 5 any one method, wherein the circulation with step (1) to (4) repeats at least once.
7, according to the top the 2nd to 5 any one method, wherein the described aromatic carbonate that obtains in step (4) is a carbonate alkyl aryl ester, and this method further comprises the following steps (5) afterwards in step (4):
(5) described carbonate alkyl aryl ester is carried out disproportionation reaction, obtain diaryl carbonate.
8,, wherein in step (5), will be recycled to step (4) with the dialkyl carbonate that described diaryl carbonate generates according to top the 7th method.
9, according to top the 7th or 8 method, wherein the circulation with step (1) to (5) repeats at least once.
10, according to the top the 1st to 9 any one method, wherein in step (1), the consumption of described organometallic compound is 1/200 to 1 times with respect to the stoichiometric quantity of the amount of described carbonic acid gas.
11, according to the top the 1st to 10 any one method, wherein described in the step (1) is reflected under 20 ℃ or the higher temperature and carries out.
12, according to the top the 1st to 11 any one method, wherein the described organometallic compound that uses in step (1) is the organometallic compound with metal-oxygen-carbon key.
13, according to top the 12nd method, the described organometallic compound that wherein has the metal-oxygen-carbon key comprises at least a following compound that is selected from:
Organometallic compound by formula (1) representative:
Wherein:
M
1Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families, except the silicon;
Each R
1And R
2Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl, by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl is perhaps represented the C that does not replace or replace
6-C
20Aryl;
Each R
3And R
4Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl or by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl; With
Each a and b are 0 to 2 integers, and a+b=0 to 2, each c and d are 0 to 4 integers, and a+b+c+d=4; And
Organometallic compound by formula (2) representative:
Wherein:
Each M
2And M
3Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families independently, except the silicon;
Each R
5, R
6, R
7And R
8Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl, by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl is perhaps represented the C that does not replace or replace
6-C
20Aryl;
Each R
9And R
10Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl or by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl; With
Each e, f, g and h are 0 to 2 integers, e+f=0 to 2, and g+h=0 to 2, each i and j are 1 to 3 integers, e+f+i=3, and g+h+j=3.
14, according to the top the 1st to 13 any one method, wherein the described separation of dialkyl carbonate described in the step (2) is undertaken by at least a distillation, extraction and the filtering separation method of being selected from.
15, according to top the 14th method, wherein the described separation of dialkyl carbonate is undertaken by distillation described in the step (2).
16, according to top the 15th method, wherein the described separation of dialkyl carbonate is undertaken by thin film distillation described in the step (2).
17, according to the top the 1st to 16 any one method, wherein described the removing by membrane sepn of water described in the step (3) carried out.
18, according to top the 17th method, wherein said membrane sepn is a pervaporation.
19, according to the top the 1st to 16 any one method, wherein described the removing by distillation of water described in the step (3) carried out.
20, according to the top the 1st to 19 any one method, wherein the described alcohol that uses in step (3) is at least a following alcohol that is selected from: have straight or branched C
1-C
12The alkyl alcohol of alkyl, has C
5-C
12The cycloalkyl alcohol of cycloalkyl, has straight or branched C
2-C
12The alkenyl alcohol of thiazolinyl and having by the C that does not replace or replace
6X-C
19The C that aryl and alkyl constitute
7-C
20The aralkyl alcohol of aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl.
21, according to the top the 1st to 20 any one method, wherein the boiling point of the alcohol that uses in step (3) is higher than the boiling point of water.
22, according to top the 21st method, wherein the alcohol that uses in step (3) is at least a following alcohol that is selected from: 1-butanols, 2-methyl isophthalic acid-propyl alcohol, have straight or branched C
5-C
12The alkyl alcohol of alkyl and have a straight or branched C
4-C
12The alkenyl alcohol of thiazolinyl.
23, according to top the 21st or 22 method, wherein the boiling point of the alcohol that uses in step (3) is lower than the boiling point of the described aromatic hydroxy compound that uses in step (4).
24, according to top the 13rd method, the R in its Chinese style (1)
3And R
4And the R in the formula (2)
9And R
10In each represent normal-butyl, 2-methyl-propyl, straight or branched C independently
5-C
12Alkyl or side chain C
4-C
12Thiazolinyl.
25, according to the top the 1st to 24 any one method, wherein in step (1), described organometallic compound uses with at least a form that is selected from monomeric form, oligomeric form, polymerized form and association form.
26, according to top the 13rd, 24 and 25 any one methods, the M in its Chinese style (1)
1And the M in the formula (2)
2And M
3In each represent tin atom.
27, according to the top the 1st to 26 any one method, wherein the described organometallic compound that uses in step (1) is by organotin oxides and alcohol preparation.
28, according to the top the 1st to 27 any one method, wherein the amount of the described aromatic hydroxy compound that uses in step (4) is with respect to the stoichiometric quantity of the amount of the described dialkyl carbonate of use in step (4) 0.1 to 10,000 times.
29, according to the top the 1st to 28 any one method, wherein described in the step (4) is reflected under 50 to 350 ℃ the temperature and carries out.
30, according to the top the 1st to 29 any one method, wherein described being reflected under the catalyst for ester exchange reaction existence in the step (4) carried out.
31, according to the top the 7th to 30 any one method, wherein described being reflected under the disproportionation reaction catalyzer existence in the step (5) carried out.
32, according to the top the 1st to 31 any one method, wherein said aromatic hydroxy compound is represented by following formula (3):
ArOH (3) wherein Ar is C
5-C
30Aromatic group.
33, according to top the 32nd method, wherein the described aromatic hydroxy compound by formula (3) representative is a phenol.
34, according to the top the 1st to 33 any one method, wherein the total content in the described alcohol that uses in step (3) of aromatic hydroxy compound and carboxylated compound is 1,000ppm or lower.
35, the aromatic carbonate of producing by the top the 1st to 34 any one method.
36, use polycarbonate, isocyanic ester or the polycarbonate diol of top the 35th aromatic carbonate production.
37, according to top the 36th polycarbonate, isocyanic ester or polycarbonate diol, wherein said aromatic carbonate is a diaryl carbonate.
Describe the present invention below in detail.
The inventive method comprises following four steps (1) to (4):
(1) carry out reaction between organometallic compound and the carbonic acid gas, obtain containing the reaction mixture of the dialkyl carbonate that generates by this reaction,
(2) from described reaction mixture, isolate described dialkyl carbonate, obtain residual liquid,
(3) make described residual liquid and alcohol reaction, generate at least a organometallic compound, also generate water, from described organometallic compound, remove described water and
(4) make the described dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.
About step (3) and (4), these steps are carried out after step (1) and (2) are undertaken by this order, and wherein step (3) and (4) can side by side be carried out in any order or partially or completely.And then step (3) and (4) can side by side be carried out (for example, step (4) can begin, and carries out simultaneously with step (3) then) by this or another kind of order and part after step (3) beginning.Step (3) uses different equipment to carry out respectively with (4).
About each step in the step (1) to (3), its summary of explained later.In step (1), carry out reaction by following formula (6) representative.
That is to say, in step (1), carry out the reaction between organometallic compound and the carbonic acid gas, generate the CO of organometallic compound
2Adducts carries out CO then
2The pyrolysis of adducts obtains containing the reaction mixture of dialkyl carbonate thus.This reaction mixture not only contains dialkyl carbonate, and contains the metallic components that generates from organometallic compound.
In step (2), as shown in the formula reacting shown in (7) and separating subsequently.
That is to say, from step (1) gained reaction mixture, separate dialkyl carbonate, obtain containing the residual liquid of metallic components thus.
In step (3), carry out reaction (that is to say, wherein generate the reaction of at least a organometallic compound and water), and from organometallic compound, remove and anhydrate by residual liquid (containing metallic components) and alcohol by following formula (8) representative.
In step (3), preferably, make therefrom and be recycled to step (1) except that the organometallic compound that anhydrates.
About step (4), give an explaination below.In step (4), make the dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.Generally speaking, by the reaction of dialkyl carbonate and aromatic hydroxy compound, generate carbonate alkyl aryl ester and alcohol (formula (9) as follows).
For example, this reaction can be carried out with catalyzer, takes out dialkyl carbonate and alcohol simultaneously from reaction system.Carbonate alkyl aryl ester and aromatic hydroxy compound reaction generate diaryl carbonate and alcohol (formula (10) as follows).
Carbonate alkyl aryl ester also experiences disproportionation reaction, generates diaryl carbonate and dialkyl carbonate (formula (11) as follows).
For example, the disproportionation reaction of carbonate alkyl aryl ester can be carried out with catalyzer, takes out carbonate alkyl aryl ester simultaneously from reaction system.
Thereby in step (4),, can obtain required aromatic carbonate by the control reaction conditions.That is to say, for example can mainly obtain carbonate alkyl aryl ester as aromatic carbonate.Select as an alternative, also can mainly obtain diaryl carbonate as aromatic carbonate.And then also the mixture that can obtain carbonate alkyl aryl ester and diaryl carbonate is as aromatic carbonate, and wherein the difference between the amount of the amount of carbonate alkyl aryl ester and diaryl carbonate is less.
As mentioned above, in step (4),, generate carbonate alkyl aryl ester and alcohol by the reaction between dialkyl carbonate and the aromatic hydroxy compound.Preferably, make the alcohol that is generated be recycled to step (3).
And then as mentioned above, in step (4), can generate dialkyl carbonate by the above-mentioned disproportionation reaction of carbonate alkyl aryl ester.And then in step (4), about the dialkyl carbonate (it is separated in step (2)) that is used for reacting with aromatic hydroxy compound, its part is unreacted still.Preferably, make these dialkyl carbonates (the just dialkyl carbonate that generates by disproportionation reaction and the still dialkyl carbonate of unreacted) be recycled to step (4).
In the methods of the invention, preferably, the circulation of step (1) to (4) repeats at least once.
Preferably, step (4) gained aromatic carbonate is a carbonate alkyl aryl ester, and the inventive method further comprises the following steps (5) afterwards in step (4):
(5) make described carbonate alkyl aryl ester carry out disproportionation reaction, obtain diaryl carbonate.
The reaction of carrying out in step (5) is the reaction by following formula (11) representative, just wherein generates the reaction of diaryl carbonate and dialkyl carbonate by the disproportionation reaction of carbonate alkyl aryl ester.Preferably, the dialkyl carbonate that is generated is recycled to step (4).
When the inventive method comprised step (5) and step (1) to (4), preferably, the circulation of step (1) to (5) repeated at least once.
Thereby, in the optimal way of the inventive method, carry out step (1) to (4), make organometallic compound (it generates in step (3)) and alcohol (it generates in step (4)) be recycled to step (1) and (3) respectively simultaneously.In this optimal way of the inventive method,, wherein do not use other raw material beyond removing carbon dioxide and the aromatic hydroxy compound basically from only obtain aromatic carbonate and water as the carbonic acid gas of raw material and aromatic hydroxy compound as product.That is to say, produce the total reaction scheme of aromatic carbonate by this optimal way of the inventive method and can represent by following formula (12).
Below, between the above-mentioned optimal way of the inventive method and ordinary method, compare, as the inventive method, ordinary method also uses carbonic acid gas as the carbonyl source.
The optimal way of the inventive method relates to the reaction by following formula (12) representative, and it is different from following use carbonic acid gas any one as the ordinary method (a) and (b) in carbonyl source and (c) fully:
A) by the method for ethylene oxide etc. and carbon dioxide production aromatic carbonate, wherein via the cyclic carbonate that generates as intermediate product;
B) method of production dialkyl carbonate is wherein used organic dewatering agent; With
C) method of production dialkyl carbonate is wherein used solid dewatering agent (inorganic dewatering agent).
At first interpretation procedure a) and the difference between the above-mentioned optimal way of the inventive method.Should be appreciated that, method a) in, by produce aromatic carbonate (the total reaction scheme that relates to the production aromatic carbonate of formula (13) to (17) reaction can be by following formula (18) representative) by the reaction sequence of following formula (13) to (17) representative.
In following formula (15) and (16) reaction, produce alcohol.Make these alcohol be recycled to the reaction system of formula (14) reaction, be used for producing dialkyl carbonate from ethylene carbonate and alcohol.In this respect, method a) is different from optimal way of the present invention, wherein makes the pure recirculation that generates as intermediate product be used to produce organometallic compound.And then, aromatic carbonate production method total reaction scheme a) (is just wherein produced the reaction scheme of aromatic carbonate and ethylene glycol) as the formula (18) from carbonic acid gas, ethylene oxide and aromatic hydroxy compound, this reaction scheme is different from following formula (12) reaction fully, and the latter is that the above-mentioned optimal way by the inventive method carries out.Therefore, method a) is different from the optimal way of the inventive method fully.
About method b), this is a kind ofly to produce dialkyl carbonate but not the method for aromatic carbonate.With regard to information, explained later method b) and the difference between the inventive method optimal way but.At method b) in, balanced reaction by following formula (4) representative generates dialkyl carbonate and water, and make the water and organic dewatering agent (the being acetal) reaction (being formula (5) reaction) that are generated, so that the balance of formula (4) reaction moves to forming required product direction, increase the amount of the dialkyl carbonate of being produced thus.Therefore should be appreciated that, at method b) in, by the reaction generation dialkyl carbonate of following formula (19) representative, wherein supervene organic dewatering agent with dialkyl carbonate, wherein the amount of organic dewatering agent and dialkyl carbonate are equimolar.
Formula (19) reacts completely and is different from formula (12) reaction, and the latter is that the above-mentioned optimal way by the inventive method carries out.Therefore, method b) be different from the optimal way of the inventive method fully.
Can imagine, make by method b) dialkyl carbonate and aromatic hydroxy compound reaction generation aromatic carbonate and the alcohol that obtain.In this case, when planning to make the pure recirculation of supervening with aromatic carbonate, suppose that this alcohol is used for the regeneration of organic dewatering agent (being acetal).And in this respect, obvious method b) be different from the optimal way of the inventive method fully, in the latter, make the pure recirculation that generates as intermediate product be used for the regeneration of organometallic compound.
About method c) difference between (just produce the method for dialkyl carbonate, wherein use the solid dewatering agent) and the inventive method optimal way, give an explaination below.The situation of (as method b), method c) also be to produce dialkyl carbonate but not the method for aromatic carbonate.But, with regard to information, provide below about method c) explanation.) at method c) and in to be used to produce reaction that dialkyl carbonate carries out be balanced reaction by following formula (20) representative.
Can be by the water that formula (20) reaction generates with solid dewatering agent (inorganic dewatering agent) reaction or by its absorption, the balance of formula (20) reaction moves to the direction that generates required product thus, increases the productive rate of dialkyl carbonate thus.But, formula (20) reacts completely and is different from formula (12) reaction, and the latter is that the above-mentioned optimal way by the inventive method carries out.Therefore, method c) be different from the optimal way of the inventive method fully.
Can imagine, make by method c) dialkyl carbonate and aromatic hydroxy compound reaction generation aromatic carbonate and the alcohol that obtain.In this case, when planning to make the pure recirculation of supervening with aromatic carbonate, suppose that this alcohol is used as the raw material of formula (20) reaction to produce aromatic carbonate.And in this respect, obvious method c) be different from the optimal way of the inventive method fully, in the latter, make the pure recirculation that generates as intermediate product be used for the regeneration of organometallic compound.
Below, carry out explanation about compound used therefor of the present invention.
Organometallic compound about using in the inventive method step (1) has no particular limits, as long as it and carbon dioxide reaction generation dialkyl carbonate.But, preferred use has the organometallic compound of metal-oxygen-carbon key, for example has the organometallic compound of alkoxyl group.Have the organometallic compound of metal-oxygen-carbon key about this class, preferably, this organometallic compound comprises at least a following compound that is selected from:
Organometallic compound by formula (1) representative:
Wherein:
M
1Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families, except the silicon;
Each R
1And R
2Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl is by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20Aralkyl, the perhaps C that does not replace or replace
6-C
20Aryl;
Each R
3And R
4Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl is perhaps by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20Aralkyl; With
Each a and b are 0 to 2 integers, and a+b=0 to 2, each c and d are 0 to 4 integers, and a+b+c+d=4; And
Organometallic compound by formula (2) representative:
Wherein:
Each M
2And M
3Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families independently, except the silicon;
Each R
5, R
6, R
7And R
8Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl is by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20Aralkyl, the perhaps C that does not replace or replace
6-C
20Aryl;
Each R
9And R
10Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl is perhaps by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20Aralkyl; With
Each e, f, g and h are 0 to 2 integers, e+f=0 to 2, and g+h=0 to 2, each i and j are 1 to 3 integers, e+f+i=3, and g+h+j=3.
Periodictable mentioned in this article is that IUPAC (International Union of Pure and Applied Chemistry(IUPAC)) naming system (1989) is specified.
Above-mentioned organometallic compound uses with at least a form that is selected from monomeric form, oligomeric form, polymerized form and association form.
As mentioned above, the M in the formula (1)
1And the M in the formula (2)
2And M
3In each represent the atoms metal that is selected from the element that belongs to periodictable the 4th and 14 families independently, except the silicon.Preferably, M
1, M
2And M
3In each be the atoms metal that is selected from titanium atom, tin atom, nickle atom, cobalt atom and zirconium atom.For the solvability in alcohol and with reactive consideration of alcohol, more preferably, M
1, M
2And M
3In each be the metal that is selected from titanium atom and tin atom, most preferably, M
1, M
2And M
3In each be tin atom.
R in the formula (1)
1With R
2And the R in the formula (2)
5, R
6, R
7With R
8Example comprise C
1-C
12Alkyl and C
5-C
12Cycloalkyl, for example methyl, ethyl, propyl group (and isomer), butyl (and isomer), amyl group (and isomer), hexyl (and isomer), heptyl (and isomer), octyl group (and isomer), nonyl (and isomer), butenyl (and isomer), pentenyl (and isomer), cyclobutyl, cyclopentyl, cyclopentadienyl and cyclohexenyl; C
7-C
20Aralkyl, for example benzyl and styroyl; And C
6-C
20Aryl, for example phenyl, tolyl and naphthyl.In these alkyl each can not replaced with carbonic acid gas or the pure group (for example alkoxyl group, dialkyl amido or alkoxy carbonyl) that reacts.And then each in these alkyl can have ehter bond.And each in these alkyl can be halogenated alkyl (just its at least one hydrogen atom is by the displaced alkyl of halogen atom), for example nine fluorine butyl or seven fluorine butyl (and isomer).But, R
1, R
2, R
5, R
6, R
7And R
8Be not limited to these examples.In the above-mentioned group, preferred low alkyl group, for example C
1-C
8Alkyl, more preferably straight or branched C
1-C
4Alkyl.The alkyl that has than above-mentioned more carbon atom also can be used as R
1, R
2, R
5, R
6, R
7And R
8But, when using this class to have the group of bigger number of carbon atoms, the danger that exists the productivity of the flowability of organometallic compound and/or aromatic carbonate to reduce.
R in the formula (1)
3With R
4And the R in the formula (2)
9With R
10Example comprise C
1-C
12Alkyl and C
5-C
12Cycloalkyl, for example methyl, ethyl, propyl group (and isomer), butyl (and isomer), amyl group (and isomer), hexyl (and isomer), cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, methoxy ethyl and ethoxyl methyl; And C
7-C
20Aralkyl, for example benzyl and styroyl.In the above-mentioned group, preferred low alkyl group.
About by the alkoxyl group of the organometallic compound of following formula (1) and (2) representative (just in the formula (1)-OR
3With-OR
4And in the formula (2)-OR
9With-OR
10), preferably, the alcohol of each correspondence (R just
3OH, R
4OH, R
9OH and R
10OH) boiling point is higher than the boiling point (wherein this boiling point is under atmospheric pressure measured) of water, and the alkyl or alkenyl of each alkoxyl group partly is normal-butyl, 2-methyl-propyl, straight or branched C
5-C
12Alkyl or side chain C
4-C
12Thiazolinyl.And then, for making in step (3) the organometallic compound recirculation of reclaiming and effectively carrying out the consideration of the reaction of step (4), more preferably, the boiling point of the alcohol of each above-mentioned correspondence is lower than the boiling point (wherein this boiling point is under atmospheric pressure measured) of the used aromatic hydroxy compound of step (4), and the moieties of above-mentioned alkoxyl group is normal-butyl, 2-methyl-propyl or straight or branched C
5-C
8Alkyl.Most preferably, the moieties of above-mentioned alkoxyl group does not have branched structure on alpha-carbon atom (just being present in the carbon atom in the metal-oxygen-carbon key of organometallic compound).The example of this class moieties comprises normal-butyl, 2-methyl-propyl and straight or branched C
5-C
6Alkyl.
Example by the organometallic compound of following formula (1) representative comprises alkoxyl group tin compound, alkoxy titanium compound and alkyl alkoxy tin compound.The specific examples of this class organometallic compound comprises tetramethoxy tin, tin tetraethoxide, four propoxy-tin (and isomer), four butoxy tin (and isomer), four pentyloxy tin (and isomer), four hexyloxy tin (and isomer), four oxygen base tin in heptan (and isomer), four octyloxy tin (and isomer), four oxygen base tin in the ninth of the ten Heavenly Stems (and isomer), dimethoxy diethoxy tin, the tetramethoxy titanium, purity titanium tetraethoxide, four titanium propanolates, tetraisopropoxy titanium, four (2-ethyl-1-hexyloxy) titanium, benzyloxy-4 tin, diethoxy dipropoxy tin (and isomer), dimethoxy two hexyloxy tin (and isomer), dimethylformamide dimethyl oxygen base tin, dimethyl diethoxy tin, dimethyl dipropoxy tin (and isomer), dimethyl dibutoxy tin (and isomer), dimethyl two pentyloxy tin (and isomer), dimethyl two hexyloxy tin (and isomer), dimethyl oxygen base in two heptan tin (and isomer), dimethyl two octyloxy tin (and isomer), dimethyl oxygen base in two ninth of the ten Heavenly Stems tin (and isomer), dimethyl didecyl oxygen base tin (and isomer), methyl butyl tin diformazan alcoholate, methyl butyl tin diethyl alcoholate, methyl butyl tin two propoxy-s (and isomer), methyl butyl tin two fourth alcoholate (and isomer), methyl butyl tin diamyl alcoholate (and isomer), methyl butyl tin two own alcoholate (and isomer), methyl butyl tin alcoholate in two heptan (and isomer), methyl butyl tin two hot alcoholate (and isomer), ethyl-butyl tin diformazan alcoholate, ethyl-butyl tin diethyl alcoholate, ethyl-butyl tin two propoxy-s (and isomer), ethyl-butyl tin two fourth alcoholate (and isomer), ethyl-butyl tin diamyl alcoholate (and isomer), ethyl-butyl tin two own alcoholate (and isomer), ethyl-butyl tin alcoholate in two heptan (and isomer), ethyl-butyl tin two hot alcoholate (and isomer), propyl group butyl tin diformazan alcoholate, propyl group butyl tin diethyl alcoholate, propyl group butyl tin two propoxy-s (and isomer), propyl group butyl tin two fourth alcoholate (and isomer), propyl group butyl tin diamyl alcoholate (and isomer), propyl group butyl tin two own alcoholate (and isomer), propyl group butyl tin alcoholate in two heptan (and isomer), propyl group butyl tin two hot alcoholate (and isomer), dibutyl tin diformazan alcoholate, dibutyl tin diethyl alcoholate, dibutyl tin two propoxy-s (and isomer), dibutyl tin two fourth alcoholate (and isomer), dibutyl tin diamyl alcoholate (and isomer), dibutyl tin two own alcoholate (and isomer), dibutyl tin alcoholate in two heptan (and isomer), dibutyl tin two hot alcoholate (and isomer), dibutyl tin alcoholate in two ninth of the ten Heavenly Stems (and isomer), dibutyl tin didecyl alcoholate (and isomer), dibutyl tin dibenzyl alcoholate, dibutyl tin hexichol ethylate, tin diphenyl diformazan alcoholate, tin diphenyl diethyl alcoholate, tin diphenyl two propoxy-s (and isomer), tin diphenyl two fourth alcoholate (and isomer), tin diphenyl diamyl alcoholate (and isomer), tin diphenyl two own alcoholate (and isomer), tin diphenyl alcoholate in two heptan (and isomer), tin diphenyl two hot alcoholate (and isomer), tin diphenyl alcoholate in two ninth of the ten Heavenly Stems (and isomer), tin diphenyl didecyl alcoholate (and isomer), tin diphenyl dibenzyl alcoholate, tin diphenyl hexichol ethylate, two (trifluoro butyl) tin diformazan alcoholate, two (trifluoro butyl) tin diethyl alcoholate, two (trifluoro butyl) tin two propoxy-s (and isomer), two (trifluoro butyl) tin two fourth alcoholate (and isomer), two (trifluoro butyl) tin diamyl alcoholate (and isomer), two (trifluoro butyl) tin two own alcoholate (and isomer), two (trifluoro butyl) tin alcoholate in two heptan (and isomer), two (trifluoro butyl) tin two hot alcoholate (and isomer), two (trifluoro butyl) tin alcoholate in two ninth of the ten Heavenly Stems (and isomer), two (trifluoro butyl) tin didecyl alcoholate (and isomer), two (trifluoro butyl) tin dibenzyl alcoholate, two (trifluoro butyl) tin hexichol ethylate, two (five fluorine butyl) tin diformazan alcoholate, two (five fluorine butyl) tin diethyl alcoholate, two (five fluorine butyl) tin two propoxy-s (and isomer), two (five fluorine butyl) tin two fourth alcoholate (and isomer), two (five fluorine butyl) tin diamyl alcoholate (and isomer), two (five fluorine butyl) tin two own alcoholate (and isomer), two (five fluorine butyl) tin alcoholate in two heptan (and isomer), two (five fluorine butyl) tin two hot alcoholate (and isomer), two (five fluorine butyl) tin alcoholate in two ninth of the ten Heavenly Stems (and isomer), two (five fluorine butyl) tin didecyl alcoholate (and isomer), two (five fluorine butyl) tin dibenzyl alcoholate, two (five fluorine butyl) tin hexichol ethylate, two (seven fluorine butyl) tin diformazan alcoholate, two (seven fluorine butyl) tin diethyl alcoholate, two (seven fluorine butyl) tin two propoxy-s (and isomer), two (seven fluorine butyl) tin two fourth alcoholate (and isomer), two (seven fluorine butyl) tin diamyl alcoholate (and isomer), two (seven fluorine butyl) tin two own alcoholate (and isomer), two (seven fluorine butyl) tin alcoholate in two heptan (and isomer), two (seven fluorine butyl) tin two hot alcoholate (and isomer), two (seven fluorine butyl) tin alcoholate in two ninth of the ten Heavenly Stems (and isomer), two (seven fluorine butyl) tin didecyl alcoholate (and isomer), two (seven fluorine butyl) tin dibenzyl alcoholate, two (seven fluorine butyl) tin hexichol ethylate, two (nine fluorine butyl) tin diformazan alcoholate, two (nine fluorine butyl) tin diethyl alcoholate, two (nine fluorine butyl) tin two propoxy-s (and isomer), two (nine fluorine butyl) tin two fourth alcoholate (and isomer), two (nine fluorine butyl) tin diamyl alcoholate (and isomer), two (nine fluorine butyl) tin two own alcoholate (and isomer), two (nine fluorine butyl) tin alcoholate in two heptan (and isomer), two (nine fluorine butyl) tin two hot alcoholate (and isomer), two (nine fluorine butyl) tin alcoholate in two ninth of the ten Heavenly Stems (and isomer), two (nine fluorine butyl) tin didecyl alcoholate (and isomer), two (nine fluorine butyl) tin dibenzyl alcoholate and two (nine fluorine butyl) tin hexichol ethylate.
Example by the organometallic compound of following formula (2) representative comprises alkoxyl group distannoxane and aralkoxy distannoxane.The specific examples of this class organometallic compound comprises:
1,1,3,3-tetramethyl--1,3-dimethoxy distannoxane,
1,1,3,3-tetramethyl--1,3-diethoxy distannoxane,
1,1,3,3-tetramethyl--1,3-dipropoxy distannoxane (and isomer),
1,1,3,3-tetramethyl--1,3-dibutoxy distannoxane (and isomer),
1,1,3,3-tetramethyl--1,3-two pentyloxy distannoxanes (and isomer),
1,1,3,3-tetramethyl--1,3-two hexyloxy distannoxanes (and isomer),
1,1,3,3-tetramethyl--1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3,3-tetramethyl--1,3-two octyloxy distannoxanes (and isomer),
1,1,3,3-tetramethyl--1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3,3-tetramethyl--1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3,3-tetramethyl--1,3-benzyloxy distannoxane,
1,1,3,3-tetramethyl--1,3-hexichol oxyethyl group distannoxane,
1,3-dibutyl-1,3-dimethyl-1,3-dimethoxy distannoxane,
1,3-dibutyl-1,3-dimethyl-1,3-diethoxy distannoxane,
1,3-dibutyl-1,3-dimethyl-1,3-dipropoxy distannoxane (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-dibutoxy distannoxane (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-two pentyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-two hexyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-oxygen base in two heptan distannoxane (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-two octyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-didecyl oxygen base distannoxane (and isomer),
1,3-dibutyl-1,3-dimethyl-1,3-benzyloxy distannoxane,
1,3-dibutyl-1,3-dimethyl-1,3-hexichol oxyethyl group distannoxane,
1,3-dibutyl-1,3-diethyl-1,3-dimethoxy distannoxane,
1,3-dibutyl-1,3-diethyl-1,3-diethoxy distannoxane,
1,3-dibutyl-1,3-diethyl-1,3-dipropoxy distannoxane (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-dibutoxy distannoxane (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-two pentyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-two hexyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-oxygen base in two heptan distannoxane (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-two octyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-didecyl oxygen base distannoxane (and isomer),
1,3-dibutyl-1,3-diethyl-1,3-benzyloxy distannoxane,
1,3-dibutyl-1,3-diethyl-1,3-hexichol oxyethyl group distannoxane,
1,3-dibutyl-1,3-dipropyl-1,3-dimethoxy distannoxane,
1,3-dibutyl-1,3-dipropyl-1,3-diethoxy distannoxane,
1,3-dibutyl-1,3-dipropyl-1,3-dipropoxy distannoxane (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-dibutoxy distannoxane (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-two pentyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-two hexyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-oxygen base in two heptan distannoxane (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-two octyloxy distannoxanes (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-didecyl oxygen base distannoxane (and isomer),
1,3-dibutyl-1,3-dipropyl-1,3-benzyloxy distannoxane,
1,3-dibutyl-1,3-dipropyl-1,3-hexichol oxyethyl group distannoxane,
1,1,3, the 3-tetrabutyl-1,3-dimethoxy distannoxane,
1,1,3, the 3-tetrabutyl-1,3-diethoxy distannoxane,
1,1,3, the 3-tetrabutyl-1,3-dipropoxy distannoxane (and isomer),
1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane (and isomer),
1,1,3, the 3-tetrabutyl-1,3-two pentyloxy distannoxanes (and isomer),
1,1,3, the 3-tetrabutyl-1,3-two hexyloxy distannoxanes (and isomer),
1,1,3, the 3-tetrabutyl-1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3, the 3-tetrabutyl-1,3-two octyloxy distannoxanes (and isomer),
1,1,3, the 3-tetrabutyl-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3, the 3-tetrabutyl-1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3, the 3-tetrabutyl-1,3-benzyloxy distannoxane,
1,1,3, the 3-tetrabutyl-1,3-hexichol oxyethyl group distannoxane,
1,1,3,3-tetraphenyl-1,3-dimethoxy distannoxane,
1,1,3,3-tetraphenyl-1,3-diethoxy distannoxane,
1,1,3,3-tetraphenyl-1,3-dipropoxy distannoxane (and isomer),
1,1,3,3-tetraphenyl-1,3-dibutoxy distannoxane (and isomer),
1,1,3,3-tetraphenyl-1,3-two pentyloxy distannoxanes (and isomer),
1,1,3,3-tetraphenyl-1,3-two hexyloxy distannoxanes (and isomer),
1,1,3,3-tetraphenyl-1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3,3-tetraphenyl-1,3-two octyloxy distannoxanes (and isomer),
1,1,3,3-tetraphenyl-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3,3-tetraphenyl-1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3,3-tetraphenyl-1,3-benzyloxy distannoxane,
1,1,3,3-tetraphenyl-1,3-hexichol oxyethyl group distannoxane,
1,1,3,3-four (trifluoro butyl)-1,3-dimethoxy distannoxane,
1,1,3,3-four (trifluoro butyl)-1,3-diethoxy distannoxane,
1,1,3,3-four (trifluoro butyl)-1,3-dipropoxy distannoxane (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-dibutoxy distannoxane (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-two pentyloxy distannoxanes (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-two hexyloxy distannoxanes (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-two octyloxy distannoxanes (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3,3-four (trifluoro butyl)-1,3-benzyloxy distannoxane,
1,1,3,3-four (trifluoro butyl)-1,3-hexichol oxyethyl group distannoxane,
1,1,3,3-four (five fluorine butyl)-1,3-dimethoxy distannoxane,
1,1,3,3-four (five fluorine butyl)-1,3-diethoxy distannoxane,
1,1,3,3-four (five fluorine butyl)-1,3-dipropoxy distannoxane (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-dibutoxy distannoxane (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-two pentyloxy distannoxanes (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-two hexyloxy distannoxanes (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-two octyloxy distannoxanes (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3,3-four (five fluorine butyl)-1,3-benzyloxy distannoxane,
1,1,3,3-four (five fluorine butyl)-1,3-hexichol oxyethyl group distannoxane,
1,1,3,3-four (seven fluorine butyl)-1,3-dimethoxy distannoxane,
1,1,3,3-four (seven fluorine butyl)-1,3-diethoxy distannoxane,
1,1,3,3-four (seven fluorine butyl)-1,3-dipropoxy distannoxane (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-dibutoxy distannoxane (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-two pentyloxy distannoxanes (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-two hexyloxy distannoxanes (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-two octyloxy distannoxanes (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3,3-four (seven fluorine butyl)-1,3-benzyloxy distannoxane,
1,1,3,3-four (seven fluorine butyl)-1,3-hexichol oxyethyl group distannoxane,
1,1,3,3-four (nine fluorine butyl)-1,3-dimethoxy distannoxane,
1,1,3,3-four (nine fluorine butyl)-1,3-diethoxy distannoxane,
1,1,3,3-four (nine fluorine butyl)-1,3-dipropoxy distannoxane (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-dibutoxy distannoxane (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-two pentyloxy distannoxanes (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-two hexyloxy distannoxanes (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-oxygen base in two heptan distannoxane (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-two octyloxy distannoxanes (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-oxygen base in two ninth of the ten Heavenly Stems distannoxane (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-didecyl oxygen base distannoxane (and isomer),
1,1,3,3-four (nine fluorine butyl)-1,3-benzyloxy distannoxane and
1,1,3,3-four (nine fluorine butyl)-1,3-hexichol oxyethyl group distannoxane.
Above-mentioned organometallic compound can separately or be united use.And then organometallic compound except that above-mentioned and optional inorganic metal can be united use with any above-mentioned organometallic compound.As organometallic compound, can use commercial those that obtain.Select as an alternative, can produce organometallic compound by ordinary method.For example, can produce organometallic compound, wherein make oxidation organotin and alcohol reaction, obtain organometallic compound by a kind of like this method.Particularly, for example,, can obtain having dibutyl tin two alcoholate of long-chain alkoxy base from dibutyltin oxide and long-chain alcohol by the described method of German Patent No.6612421.Also can obtain dialkyl tin two alcoholate from halo dialkyl tin (for example dichloro dialkyl tin) and alcoholization sodium etc.And then, by above-mentioned WO 03/055840 or WO 04/014840 described method, also can obtain the dialkyl tin alcoholate from oxidation dialkyl tin and lower alcohol.In WO 03/055840 or WO 04/014840 described method, when the alcohol that is lower than the boiling point of water from dibutyltin oxide and boiling point obtained organometallic compound, the gained organometallic compound was tending towards mainly being made of the organometallic compound by formula (2) representative.But, if necessary, can obtain in a large number organometallic compound in the following way: the above-mentioned organometallic compound that mainly is made of the organometallic compound by formula (2) representative is distilled, obtain organometallic compound thus by formula (1) representative as distillate by formula (1) representative.
Respectively by the organometallic compound of formula (1) and (2) representative can by tin-119 nucleus magnetic resonance (
119Sn-NMR) spectrum is differentiated (for example referring to U.S. Patent No. 5,545,600).But, known
119In the Sn-NMR spectrum, differ widely owing to the chemical drifting value by the organometallic compound structure of formula (1) representative, this for example depends on and is used for
119The organometallic compound content of the sample that Sn-NMR analyzes and being used for
119The existence of alcohol whether (this fact is not mentioned in above-mentioned U.S. Patent No. 5,545,600) in the sample that Sn-NMR analyzes.The analysis that it is therefore preferable that organometallic compound is undertaken by a kind of like this method, in the method, and with above-mentioned
119Sn-NMR spectrum unite use proton magnetic resonance (PMR) (
1H-NMR) spectrum and 13C nuclear magnetic resonance (
13C-NMR) spectrum.
In the present invention, as mentioned above preferably, organometallic compound comprises at least a organometallic compound of free style (1) representative and the compound of the organometallic compound that formula (2) is represented of selecting.Can obtain dialkyl carbonate from one of formula (1) organometallic compound and formula (2) organometallic compound.But, for the consideration of the productive rate of the generating rate of dialkyl carbonate and dialkyl carbonate, preferably use formula (1) organometallic compound.Particularly, preferred use formula (1) organometallic compound separately or use the combination of itself and other kind organometallic compound, make based on the integral molar quantity of institute's containing metal in the used organometallic compound of the present invention and by the mol% of institute's containing metal in formula (1) organometallic compound, formula (1) organometallic compound be 50mol% or more than.
Below, provide explanation about the used alcohol of the inventive method.
In the methods of the invention, in step (3), use first kind of alcohol.In addition, second kind of alcohol can be randomly in step (1), used, and the third alcohol can be randomly in step (2), used.
First, second and the third alcohol each other can be identical or different.The example of this class alcohol comprises having straight or branched C
1-C
12The alkyl alcohol of alkyl has C
5-C
12The cycloalkyl alcohol of cycloalkyl has straight or branched C
2-C
12The alkenyl alcohol of thiazolinyl and having by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20The aralkyl alcohol of aralkyl.
These pure specific exampless comprise C
1-C
12Fatty alcohol and C
5-C
12Alicyclic alcohol, for example methyl alcohol, ethanol, propyl alcohol, the 2-propyl alcohol, the 1-butanols, 2-butanols (and isomer), 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol, cyclobutanol, the 1-amylalcohol, 2-amylalcohol (and isomer), the 3-amylalcohol, 3-methyl isophthalic acid-butanols, 2-methyl-1-butene alcohol, 2-methyl-2-butanols (and isomer), 3-methyl-2-butanols (and isomer), cyclopentanol, 2-methyl isophthalic acid-cyclobutanol (and isomer), 3-methyl isophthalic acid-cyclobutanol (and isomer), 1-methyl isophthalic acid-cyclobutanol (and isomer), cyclobutanemethanol (and isomer), the 1-hexanol, 2-hexanol (and isomer), 3-hexanol (and isomer), 4-methyl-1-pentene alcohol (and isomer), 3-methyl-1-pentene alcohol (and isomer), 2-methyl-1-pentene alcohol (and isomer), 2-ethyl-1-butanols, 3-methyl-2-amylalcohol (and isomer), 3-methyl-3-amylalcohol (and isomer), hexalin, 1-methyl isophthalic acid-cyclopentanol (and isomer), 2-methyl isophthalic acid-cyclopentanol (and isomer), 2-cyclobutyl ethanol (and isomer), 1-cyclobutyl ethanol (and isomer), (1-methyl cyclobutyl) methyl alcohol (and isomer), (2-methyl cyclobutyl) methyl alcohol (and isomer), enanthol (and isomer), hexahydrobenzyl alcohol (and isomer), (methylcyclohexyl) methyl alcohol (and isomer), cyclohexyl ethyl alcohol (and isomer), (ethyl cyclobutyl) methyl alcohol (and isomer), (methyl cyclopropyl) ethanol (and isomer), (ethyl cyclopropyl) methyl alcohol (and isomer), octanol (and isomer), nonyl alcohol (and isomer), decyl alcohol (and isomer), hendecanol (and isomer), dodecanol (and isomer), vinylcarbinol, butenol (and isomer), pentenol (and isomer), cyclopentenol (and isomer), cyclopentadiene alcohol, hexenol (and isomer) and cyclohexenol (and isomer); And aralkyl alcohol, for example benzylalcohol and phenylethyl alcohol.
And then, as first, second and the third alcohol, can use polyvalent alcohol.Examples of polyhydric alcohols comprises polynary C
1-C
12Fatty alcohol and polynary C
5-C
12Alicyclic alcohol, ethylene glycol, 1 for example, ammediol, 1,2-propylene glycol, cyclohexane diol and pentamethylene glycol; And aralkyl alcohol, for example xylyl alcohol.
In above-mentioned alcohol, preferably boiling point is higher than those (wherein this boiling point is under atmospheric pressure measured) of the boiling point of water.The example of this class alcohol comprises 1-butanols, 2-methyl isophthalic acid-propyl alcohol, has straight or branched C
5-C
12The alkyl alcohol of alkyl, has straight or branched C
4-C
12The alkenyl alcohol of thiazolinyl, cycloalkyl alcohol and aralkyl alcohol.In these alcohol, more preferably 1-butanols, 2-methyl isophthalic acid-propyl alcohol and have straight or branched C
5-C
8The alkyl alcohol of alkyl.
Among the present invention, when by repeating step (1) when aromatic carbonate is produced in the circulation of (4), the preferred alcohol (wherein this boiling point is under atmospheric pressure measured) that uses boiling point to be lower than the boiling point of the used aromatic hydroxy compound of step (4) more preferably uses and is selected from 1-butanols, 2-methyl isophthalic acid-propyl alcohol and straight or branched C
5-C
6The primary alconol of alkyl primary alconol.
Below, provide explanation about the used aromatic hydroxy compound of the inventive method step (4).
About aromatic hydroxy compound, have no particular limits.The example of aromatic hydroxy compound comprises the aromatic hydroxy compound by following formula (3) representative:
ArOH (3)
Wherein Ar represents C
5-C
30Aromatic group.
Example by the aromatic hydroxy compound of following formula (3) representative comprises phenol; Alkylphenol, for example cresols (and isomer), xylenol (and isomer), pseudocuminol (and isomer), tetramethyl phenol (and isomer), ethylphenol (and isomer), propylphenol (and isomer), butylphenol (and isomer), diethyl phenol (and isomer), methylethyl phenol (and isomer), methyl-propyl phenol (and isomer), dipropyl phenol (and isomer), methyl butyl phenol (and isomer), amyl phenol (and isomer), hexylphenol (and isomer) and cyclohexylphenol (and isomer); Alkoxy phenol, for example methoxyphenol (and isomer) and thanatol (and isomer); And by the substituted phenol of following formula (21) representative:
Wherein A represents singly-bound; Divalent group, for example-O-,-S-,-CO-or-SO
2-; The alkylidene group that does not replace or replace by following formula (22) representative; Perhaps by the cycloalkylidene of following formula (23) representative,
Wherein each aromatic ring can be independently by replacements such as low alkyl group, lower alkoxy, ester group, hydroxyl, nitro, halogen atom, cyano group.
R wherein
11, R
12, R
13And R
14In each represent hydrogen atom, low alkyl group, cycloalkyl, aryl or aralkyl independently, wherein each low alkyl group, cycloalkyl, aryl and aralkyl are randomly replaced by halogen atom or alkoxyl group.
Wherein k is 3 to 11 integer, and each hydrogen atom (H) can be replaced by low alkyl group, aryl or halogen atom.
Specific examples by the aromatic hydroxy compound of above-mentioned formula (21) representative comprises naphthols (and isomer); The naphthols that replaces; With the heteroaromatic oxy-compound, for example pyridone (and isomer), Hydroxycoumarin (and isomer) and hydroxyquinoline (and isomer).
In above-mentioned aromatic hydroxy compound, preferably has C by above-mentioned formula (3) representative
6-C
10Aromatic group is as the aromatic hydroxy compound of aromatic group Ar, most preferably phenol.
The type of the used aromatic hydroxy compound of the present invention depends on the type of required aromatic carbonate and suitably selects.For example, when needs are produced diphenyl carbonate, use phenol as aromatic hydroxy compound; And when needs obtain the carboxylol ester, use cresols as aromatic hydroxy compound; When needs are produced carbonic acid dinaphthyl ester, use naphthols as aromatic hydroxy compound.
As mentioned above, aromatic hydroxy compound can have substituting group, for example alkyl or halogen atom.And then aromatic hydroxy compound can be heterogeneous ring compound, for example pyridone.
Each step about the inventive method provides more detailed explanation below.
As mentioned above, in step (1), make organometallic compound and carbon dioxide reaction, generate the CO of organometallic compound
2Adducts carries out CO then
2The pyrolysis of adducts obtains containing the reaction mixture (seeing following formula (6)) of dialkyl carbonate thus.
The temperature of the reaction in the step (1) generally is 20 ℃ (room temperatures) or higher, preferred 20 to 300 ℃.In order to finish reaction at short notice, more preferably under 80 to 200 ℃, react.Reaction in the step (1) was generally carried out 10 minutes to 500 hours.
In step (1), preferably, the consumption of carbonic acid gas is 1 to 200 times with respect to the stoichiometric quantity of organometallic compound amount.When having greatly excessive carbon dioxide when use alcohol (second kind of alcohol) and the reaction system in step (1) in step (1) in, the balance of the reaction in the step (1) (being following formula (6) reaction) further moves to the direction that generates required product; But, also produce metallic components in a large number, and metallic components that is produced and alcohol reaction, causing the generation of free-water thus, this can reduce the productive rate of required dialkyl carbonate.Therefore, more preferably, the consumption of carbonic acid gas is 1 to 50 times with respect to the stoichiometric quantity of organometallic compound amount.And then when the amount of carbonic acid gas was big, the reaction in the step (1) became reaction under high pressure, so that not only must use high voltage bearing reaction vessel, and wasted great amount of carbon dioxide during the removing unreacted carbonic acid gas step (1) is finished after.Therefore, most preferably, the consumption of carbonic acid gas is 1 to 20 times with respect to the stoichiometric quantity of organometallic compound amount.Thereby in step (1), preferably, the consumption of organometallic compound is 1/200 to 1 times of stoichiometric quantity that is equivalent to amount of carbon dioxide, and more favourable is 1/50 to 1 times, and the most favourable is 1/20 to 1 times.
When being reflected in the step (1) carried out under room temperature (20 ℃) or the higher temperature, the solubleness of carbonic acid gas in alcohol was limited, therefore the danger that exists speed of reaction to become extremely low.Therefore, the pressure that is used for the reaction of step (1) generally be normal atmosphere to 200MPa, preferred atmosphere is depressed into 100MPa, wherein if necessary, can be when reacting introduces extra carbonic acid gas in reaction system.The introducing of additional carbon dioxide in reaction system can intermittently or be carried out continuously.
When the analysis of gained reaction mixture (it is a liquid) confirms to have obtained the required dialkyl carbonate of satisfactory amount, stop step (1).For example, when the amount of gained dialkyl carbonate is 10% or when above based on the stoichiometric quantity with respect to the organometallic compound amount, can be after the pressure in the reaction vessel be reduced to normal atmosphere, perhaps select as an alternative to need not to reduce the interior pressure of reaction vessel, from reaction vessel, take out reaction mixture.
In the methods of the invention, the reaction system in the step (1) can contain the material except that above-mentioned.Other example that can be used for the material of step (1) is included in those that serve as dewatering agent in the reaction system.By use dewatering agent in step (1), it is anhydrous that reaction system can keep.As dewatering agent, can use organic dewatering agent of any conventional.The example of dewatering agent comprises acetal compound and ortho ester, for example trimethyl orthoacetate.And then, also can use dicyclohexylcarbodiimide as organic dewatering agent.Select as an alternative, can use solid dewatering agent (for example molecular sieve) as dewatering agent.When using the solid dewatering agent, preferably, from reaction system, remove the solid dewatering agent before carrying out step (3).
In the step (1) of the inventive method, randomly use alcohol (second kind of alcohol).By using alcohol, can obtain dialkyl carbonate with high yield sometimes.Its reason is as follows.Shown in following formula (6), the reaction in the step (1) is balanced reaction, therefore has reversed reaction.By in reaction system, adding alcohol, can cause this alcohol with and the above-mentioned metallic components that generates of required alkyl carbonate between another kind of balanced reaction, suppress the progress of above-mentioned reversed reaction thus.When the second kind of alcohol that adds in reaction system contained big water gaging, the productive rate of dialkyl carbonate reduced.Therefore, preferably, the water content of second kind of alcohol is by actual amount of water and its radiometer with respect to the stoichiometric quantity of organometallic compound amount no more than 0.1, more advantageously no more than 0.01.As second kind of alcohol, can use a part to be used to produce the alcohol of organometallic compound.Provide below more specifically and explain.In production stage (1) in the process of employed organometallic compound, make alcohol and metal reaction obtain containing the reaction mixture of organic metallic compound (comprising formula (1) organometallic compound and/or formula (2) organometallic compound) and water, distillation then removes from reaction mixture and anhydrates.When a part of alcohol (in reaction mixture still unreacted) when not gasifying as yet, stops distillation.The alcohol of gasification can not be used in the step (1) as second kind of alcohol of at least a portion as yet.About second kind of pure impurities (beyond dewatering), its type and consumption are different because of the purification condition of the condition of producing second kind of alcohol and second kind of alcohol, and this purifying is optional to carry out with second kind of alcohol of recirculation.The example of this alcohol impurities comprises ether, aromatic hydroxy compound and carboxylic acid.About the impurity of the reaction in the disadvantageous effect step (1), must remove this impurity from this alcohol before being used for step (1).On the other hand, about can sharp influencing the impurity of the reaction in the step (1), needn't remove this impurity from this alcohol before being used for step (1).
For the consideration that improves dialkyl carbonate purity, as second kind of alcohol (just being used in the alcohol in the step (i)), the preferred use has and the organic group of the oxygen base (for example alkoxyl group or aralkoxy) of organometallic compound (R for example
3And R
4) alcohol of identical organic group.When this alcohol of use was pure as second kind, preferably, the amount of second kind of alcohol was 1 to 100,000 times with respect to the stoichiometric quantity of organometallic compound amount.On the other hand, the alcohol of organic group of organic group that has an oxygen base (for example alkoxyl group or aralkoxy) that is different from organometallic compound when use is as second kind when pure, perhaps when only using formula (2) organometallic compound as organometallic compound, the amount of second kind of alcohol is preferably with respect to 2 to 1 of the stoichiometric quantity of organometallic compound amount, 000 times, more preferably 10 to 1,000 times.The alcohol of organic group of organic group that has an oxygen base (for example alkoxyl group or aralkoxy) that is different from organometallic compound when use when pure, produces asymmetric dialkyl carbonate as second kind in step (1).
When making the organometallic compound that in step (3), generates be recycled to step (1), can make organometallic compound with unreacting alcohol recirculation, so that the amount of second kind of alcohol falls in the above-mentioned scope as above-mentioned second kind of alcohol.Select as an alternative, can from unreacting alcohol, separate organometallic compound, and then be circulated to step (1).
Reaction mixture after step (1) is finished can former state be used in the step (2).Select reaction mixture cooling and/or heating after in being used in step (2), before step (1) being finished as an alternative.Reaction mixture after step (1) is finished may contain carbonic acid gas, and it may be dissolved in the reaction mixture (it is a liquid), perhaps may be with the CO of organometallic compound
2The adducts form exists.Exist the shortcoming of carbonic acid gas as follows in the reaction mixture after step (1) is finished.When in step (2), distilling,, therefore there is the unexpected blistered danger of reaction mixture owing in reaction mixture, there is carbonic acid gas.Even when under reduced pressure distilling, also be difficult to keep pressure reducing horizontal constant.In order to eliminate this class shortcoming, can carry out from reaction mixture, removing the additional step of carbonic acid gas in step (2) before, wherein carbonic acid gas may be dissolved in the reaction mixture (it is a liquid), perhaps may be with organometallic CO
2The adducts form exists.As the preferred method that from reaction mixture, removes carbonic acid gas, can mention the method for pressure that the method for reaction mixture heating and reduction is contained in steps the reaction vessel (being used in the step (1)) of (1) reaction mixture after finishing.There is no need to go into details, can make the carbonic acid gas that reclaims in this CO2 removal step be recycled to step (1).
In step (2), from step (1) gained reaction mixture, isolate the dialkyl carbonate that in step (1), generates, obtain residual liquid.The dialkyl carbonate of separating in step (2) (dialkyl carbonate that generates in step (1) just) is represented by following formula (24):
R wherein
15And R
16In each represent alkyl independently, this alkyl is identical with the moieties of the alkoxyl group that the used organometallic compound of step (1) contains, its condition is when using second kind of alcohol or use the third pure in step (1) in step (2), R
15And R
16In each represent independently and be selected from following alkyl: the alkyl identical, second kind of contained alkyl of alcohol and the third pure contained alkyl with the abovementioned alkyl part of the contained alkoxyl group of organometallic compound.
The example of the dialkyl carbonate of separating in step (2) comprises methylcarbonate, diethyl carbonate, dipropyl carbonate (and isomer), carbonic acid dibutene ester (and isomer), dibutyl carbonate (and isomer), diamyl carbonate (and isomer), carbonic acid dihexyl (and isomer), carbonic acid two heptyl esters (and isomer), carbonic acid dioctyl ester (and isomer), carbonic acid ester in two ninth of the ten Heavenly Stems (and isomer), carbonic acid didecyl ester (and isomer), carbonic acid two ring pentyl esters (and isomer), carbonic acid two cyclohexyls (and isomer), carbonic acid two ring heptyl esters (and isomer), dimethyl benzyl (and isomer), dipheryl carbonate ethyl ester (and isomer), dipheryl carbonate propyl ester (and isomer), dipheryl carbonate butyl ester (and isomer), carbonic acid dichloro benzyl ester (and isomer), carbonic acid veratryl ester (and isomer), carbonic acid dimethoxy methyl ester (and isomer), carbonic acid dimethoxy ethyl ester (and isomer), carbonic acid Dichloroethyl ester (and isomer), carbonic acid dicyanoethyl ester (and isomer), the carbonic acid methyl. ethyl ester, the carbonic acid methyl. propyl diester (and isomer), the carbonic acid methyl. butyl ester (and isomer), the carbonic acid methyl. amyl group ester (and isomer), the carbonic acid ethyl. propyl diester (and isomer), the carbonic acid ethyl. butyl ester (and isomer), the carbonic acid ethyl. amyl group ester (and isomer), the carbonic acid propyl group. butyl ester (and isomer), the carbonic acid propyl group. amyl group ester (and isomer), the carbonic acid butyl. amyl group ester (and isomer), the carbonic acid butyl. polyhexamethylene (and isomer), the carbonic acid butyl. heptyl ester (and isomer) and carbonic acid butyl. octyl group ester (and isomer).
In step (2), from step (1) gained reaction mixture, separate dialkyl carbonate, obtain containing the residual liquid of metallic components.Term " residual liquid that contains metallic components " expression contains unmodified or modification, reproducible active organometallic compound residual liquid.
The separation of dialkyl carbonate can be undertaken by conventional separation method in the step (2).The example of this class separation method comprises distillation, extraction, filtration and membrane sepn.These separation methods can separately or be united use.As preferred extraction solvent, can mention not can with the solvent of dialkyl carbonate reaction.The example of this class preferred solvent comprises aliphatic hydrocrbon, for example hexane and hexanaphthene; Halohydrocarbon, for example chloroform, methylene dichloride and trichlorine methylene radical; Aromatic hydrocarbon, for example benzene, toluene and chlorobenzene; And ether, for example ether and phenylmethylether.
In step (1), when using methyl alcohol and/or ethanol as second kind when pure, perhaps when not using second kind of alcohol and organometallic compound to have methoxyl group and/or oxyethyl group, can obtain containing boiling point and be the reaction mixture of the dialkyl carbonate (for example methylcarbonate or diethyl carbonate) of 100 ℃ or lower (wherein this boiling point is under atmospheric pressure measured).Can directly separate described dialkyl carbonate by distillation from the reaction mixture Shen.Distillation can be undertaken by distillating method arbitrarily commonly used, for example under atmospheric pressure distills, under reduced pressure distills and distill under superatmospheric pressure.Distillation temperature generally is-20 ℃ of boiling points to dialkyl carbonate, preferred 20 ℃ of boiling points to dialkyl carbonate.Distillation can be undertaken in the presence of solvent or by extractive distillation.On the other hand, when the boiling point of dialkyl carbonate is higher than 100 ℃ (wherein this boiling point is under atmospheric pressure measured) or has the boiling point of six or more a plurality of carbon atom so that dialkyl carbonate when higher, the fractionation by distillation of dialkyl carbonate is sometimes with following shortcoming.When distillation temperature (just reaction mixture being carried out the distillatory temperature) when uprising, promote the reversed reaction in above-mentioned formula (6) balanced reaction greatly, reduce the productive rate of dialkyl carbonate thus.But, in this case, by separating the productive rate that dialkyl carbonate can improve dialkyl carbonate from reaction mixture, and this isolating speed is higher than the speed of reversed reaction.For this reason, the preferred employing for example depressed the distillating method that carries out in height minus, and perhaps thin film distillation method wherein increases the specific surface area of reaction mixture, so that isolate dialkyl carbonate with the steam form from reaction mixture very soon.
Device as the thin film distillation that is used for carrying out in step (2) can use any conventional device.The thin film distillation device can connect any conventional additional unit.In the present invention, the preferred thin film distillation device that has distillation tower that utilizes.As distillation tower, can use conventional equipment.
Under the situation of thin film distillation, the temperature that adopts heating surface in the thin film distillation container is as being used for isolating temperature (separation temperature).Select as an alternative, the temperature that can adopt chuck or heating medium (they are used to heat heating surface) is as separation temperature.Separation temperature is different with the metallic components that consumption and step (1) gained reaction mixture contain because of the type of dialkyl carbonate; But, separation temperature generally is that room temperature (20 ℃) is to 300 ℃.For following consideration: the balance that suppresses following formula (6) reaction moves (reversed reaction that just suppresses formula (6) balanced reaction) to original system direction, not only improve the flowability of step (1) gained reaction mixture, but also improve the flowability of each in the dialkyl carbonate and metallic components from metallic components, isolate dialkyl carbonate by thin film distillation after, preferably, separation temperature is in 80 to 180 ℃ scope.
In thin film distillation, the heating of step (1) gained reaction mixture can be undertaken by ordinary method, for example uses the method for chuck.
About the isolating pressure of thin film distillation (separating pressure), give an explaination below.When the thin film distillation device had distillation tower, the pressure that adopts the distillation tower top was as separating pressure.On the other hand, when the thin film distillation device did not have distillation tower, the internal pressure that adopts distil container was as separating pressure.Separating pressure is for example different with the metallic components that consumption and step (1) gained reaction mixture contain because of the type of dialkyl carbonate.Generally speaking, separating pressure can be decompression or normal atmosphere.Particularly, separating pressure generally is 0.1 to 101.3kPa (normal atmosphere), and preferred 0.3 to 30kPa.
When dialkyl carbonate being separated in 30kPa or more carrying out under the high pressure and dialkyl carbonate when having high boiling point from step (1) gained reaction mixture, the vapour pressure of dialkyl carbonate is lower, therefore must adopt high distillation temperature.But, when distillation temperature is higher, there is the danger of moving (that is to say that the reversed reaction of formula (6) balanced reaction takes place tempestuously) during the distillation greatly to the direction of original system that is equilibrated at of following formula (6) reaction, reduces the productive rate of dialkyl carbonate thus.Therefore, when fractionation by distillation at 30kPa or when more carrying out under the high pressure, about containing the reaction mixture of high boiling point dialkyl carbonate, necessary controlled temperature, pressure and the residence time, move to the direction of original system so that can suppress the balance of following formula (6) reaction satisfactorily.The residence time of reaction mixture in the thin film distillation container is different with the metallic components that consumption and reaction mixture contain because of the type of dialkyl carbonate; But, the residence time generally is 1 second to 1 hour.For the balance that suppresses following formula (6) reaction moves to the direction of original system, preferably, the residence time is 10 seconds to 10 minutes.The area of the heating surface in the thin film distillation container is not only different with the metallic components that consumption and reaction mixture contain because of the type of dialkyl carbonate, but also because of the material of the feeding rate of reaction mixture and thin film distillation container different.For example, can regulate the area of heating surface, so that the feeding rate of the area of heating surface and reaction mixture satisfies the relation by following formula (25) representative.
Feeding rate (g/h) * coefficient k (h * m
2/ g)=area (m of heating surface
2) (25)
Wherein coefficient k is the numerical value in from 1/10,000 to 1/1 scope, the numerical value in preferred 1/4,000 to 1/100 scope.
There is no need to go into details, based on the conventional knowledge and technology that relates to thin film distillation, can regulate the area of heating surface by the method except that the method for employing formula (25).
The thickness of formed film is not only different with the metallic components that consumption and reaction mixture contain because of the type of dialkyl carbonate during the thin film distillation of step (1) gained reaction mixture, and because of the feeding rate and the above-mentioned separation temperature of reaction mixture different; But, the thickness of film generally is 1 * 10
-8To 1 * 10
-1M.In order to improve separation efficiency, preferably, the thickness of film is 1 * 10
-6To 1 * 10
-2M.
In the present invention, must not use solvent.But, for the flowability by improving the isolating dialkyl carbonate of institute and the flowability of isolating metallic components help using the operation of step (1) gained reaction mixture, can use not the solvent that can react with dialkyl carbonate or metallic components.The preferred embodiment of this kind solvent comprises aliphatic series and clicyclic hydrocarbon, for example hexane and hexanaphthene; Halohydrocarbon, for example chloroform, methylene dichloride and trichlorine methylene radical; Aromatic hydrocarbon, for example benzene, toluene and chlorobenzene; And ether, for example ether and phenylmethylether.
In the thin film distillation device, from the cut (gaseous form) that mainly constitutes that takes out of this device, from the following taking-up residual liquid of this device by dialkyl carbonate.The cut that mainly is made of dialkyl carbonate that is taken out need not purifying and promptly can be used for step (4).Select as an alternative, be used in step (4) before at this cut, the cut that is taken out can be by the ordinary method purifying.
When the dialkyl carbonate that produces in step (1) had so high boiling point so that be difficult to the dialkyl carbonate in step (1) the gained reaction mixture separated with metallic components, separation can add alcohol (the third alcohol) and carry out in reaction mixture before the separation of the dialkyl carbonate in carrying out step (2).As the third alcohol, preferably use such alcohol: its boiling point is lower than corresponding to the boiling point of the alcohol of the contained alkoxyl group of dialkyl carbonate and is selected from alkyl, and wherein this moieties is straight or branched C
1-C
6Alkyl.Particularly, has so more lower boiling the third alcohol by in step (1) gained reaction mixture, adding, transesterification reaction takes place between dialkyl carbonate and the third alcohol, wherein the alkyl of the third pure alkyl displacement dialkyl carbonate obtains the dialkyl carbonate that boiling point is lower than the boiling point of step (1) gained dialkyl carbonate thus.Gained has more lower boiling dialkyl carbonate can easily be separated with metallic components by fractionation by distillation.
The amount of the third alcohol that adds in step (2) is different because of the reaction conditions in the step (1); But, preferably, the amount of the third alcohol is 2 to 100 by the third pure molar ratio computing with the dialkyl carbonate that generates in step (1).In step (1) gained reaction mixture, add the third pure temperature generally in the scope of room temperature (about 20 ℃) pure boiling point to the third.About the adding of the third alcohol and separating of the dialkyl carbonate that is produced by above-mentioned transesterification reaction, described adding can followingly be carried out with for example separating.Adds the third alcohol by mode in batches or continuously in step (1) gained reaction mixture, carrying out transesterification reaction, and after transesterification reaction was finished, fractionation by distillation was by the dialkyl carbonate of transesterification reaction generation.Dialkyl carbonate also can use the reactive distillation method of multistage distillation tower to carry out with separating of the third pure transesterification reaction and dialkyl carbonate in the following manner.With step (1) gained reaction mixture from it portion send into the multistage distillation tower, and the third alcohol is sent into the multistage distillation tower from its underpart, wherein transesterification reaction and distillation therein the third alcohol have under the temperature and pressure condition of vapour pressure and carry out.
Step (1) gained reaction mixture can contain the still organometallic compound of unreacted and the thermal decomposition product of organometallic compound.Step (2) can or be carried out with it after organometallic compound that removes unreacted still from step (1) gained reaction mixture and thermal decomposition product simultaneously.
As mentioned above, in step (1), make organometallic compound and carbon dioxide reaction.Because the used organometallic compound of step (1) has reactivity to carbonic acid gas, so often be called as " reactive organometallic compound " below the organometallic compound.As the inventor in above-mentioned WO 04/014840, proposed, can make step (1) gained reaction mixture contain following component: the dialkyl carbonate that generates by the reaction between organometallic compound and the carbonic acid gas; The organometallic compound of reproducible, activated, modification; With organometallic compound non-renewable, non-activity (being degradation compound).When obtaining this reaction mixture, can from step (1) gained reaction mixture, separate the organometallic compound (degradation compound) of non-renewable non-activity.Particularly, for example, the separation of degradation compound can be undertaken by a kind of like this method, wherein second mixture that step (1) gained reaction mixture is separated into first mixture that comprises dialkyl carbonate and degradation compound and comprises the residual liquid that is made of organometallic compound reproducible, activated, modification separates dialkyl carbonate again from first mixture.Select as an alternative, the separation of degradation compound can be undertaken by a kind of like this method, wherein step (1) gained reaction mixture is separated into first mixture that comprises dialkyl carbonate and comprises reproducible, activated, the organometallic compound of modification and second mixture of degradation compound, from second mixture, separate degradation compound again.
In the present invention, the term organometallic compound of modification " reproducible, activated, " is used in reference to from reactive organometallic compound derived compounds, they mainly by above-mentioned by the adducts (CO of reactive organometallic compound with the carbon dioxide reaction generation
2Adducts) or the degradation production that generates by this adducts thermolysis constitute, wherein thermal decomposition product and dialkyl carbonate generate simultaneously.Be difficult to indicate the detailed structure of the organometallic compound of reproducible, activated, modification.But, as the general example of the organometallic compound of reproducible, activated, the modification that may in the inventive method step (1), generate, can mention the hydrolysate of the carbon dioxide adduct of the hydrolysate of the above-mentioned carbon dioxide adduct of reactive organometallic compound, reactive organometallic compound and reactive organometallic compound.
On the other hand, term " organometallic compound non-renewable, non-activity " (or " degradation compound ") is used in reference to such compound, they are also derived by reactive organometallic compound, be non-renewable organic compound (thermolysis by reactive organometallic compound or its carbon dioxide adduct generates), and have extremely low activity.Degradation compound mainly generates in step (3).But, in the step of producing reactive organometallic compound, generate degradation compound sometimes.As the representative example of degradation compound, can mention such compound, each atoms metal has at least three metal-carbon keys in its molecule.As this examples for compounds, can mention compound by following formula (26) representative:
Wherein:
M
4Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families, except the silicon;
R
17, R
18And R
19In each represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl is by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20Aralkyl, the perhaps C that does not replace or replace
6-C
20Aryl;
R
20Represent straight or branched C
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl is perhaps by the C that does not replace or replace
6-C
19Aryl and be selected from straight or branched C
1-C
14Alkyl and C
5-C
14The C that the alkyl of cycloalkyl constitutes
7-C
20Aralkyl;
Each l, m and n are 0 to 4 integers, and l+m+n=3 or 4, o are 0 or 1 integers, and l+m+n+o=4.
The specific examples of following formula (26) degradation compound comprises tetraalkyl tin and trialkyltin alcoholate.Other example of degradation compound comprises organic metal oxide, for example SnO
2, TiO
2And ZrO
2
Be known that generally speaking organometallic compound carries out modifying function in the presence of oxygen.The used organometallic compound of the present invention also carries out modifying function in the presence of oxygen, generate the degradation compound except that above-mentioned degradation compound.(concrete structure of other degradation compound is not still understood.) therefore,, must suppress the amount of the oxygen contact with organometallic compound by ordinary method in the production of organometallic compound and between the shelf lives and during each step in the inventive method.
It is believed that, be that production period at following formula (1) or (2) organometallic compound generates by the degradation compound of following formula (26) representative, or by following formula (1) or (2) organometallic compound thermolysis generated.
Preferably, each step of the inventive method is carried out under the least possible condition of the amount of the degradation compound that is generated.In the methods of the invention, may generate degradation compound except that following formula (26) compound.But, in the step (2) of the inventive method, mainly remove formula (26) compound as degradation compound.Its reason is as follows.Formula (26) degradation compound (each atoms metal has at least three metal-carbon keys in its molecule) (for example has the physics that is different from useful organometallic compound (just reactive organometallic compound or organometallic compound reproducible, activated, modification) and chemical property, the boiling point of degradation compound is lower than the boiling point of useful organometallic compound, and hydrolysis is not so good as useful organometallic compound sensitivity).
Also can be except that removing by any degradation compound the degradation compound of formula (26) representative.As the preferred method of removing degradation compound, can mention discharging and filtration, they all are that generally adopt this area separately.The degradation compound that has been removed (for example formula (26) compound) can discard by ordinary method.For example, degradation compound can discard with the form that generates metal oxide by burning.There is no need to go into details, and useful organometallic compound can be regenerated from the degradation compound of being removed by ordinary method.
In step (2), even boiling point is higher than 100 ℃ dialkyl carbonate and also can be easily separates by a kind of like this method, wherein in step (1) gained reaction mixture, add entry or water-containing solvent, obtain white slurry, remove by filter the solid in the white slurry, obtain filtrate, and gained filtrate is distilled.About being used in the water in this method, have no particular limits; But, preferably use distilled water or deionized water.
In step (2), the temperature that in step (1) gained reaction mixture, adds entry from water reaction mixture not congelative temperature (for example-20 ℃) in 100 ℃ scope.After step (1) is finished, preferably, can be 10 to 80 ℃ with the temperature regulation of reaction mixture.When the dialkyl carbonate that generates in step (1) was responsive to hydrolysis, in order to suppress dialkyl carbonate generation hydrolysis satisfactorily, more preferably the temperature regulation with reaction mixture was 10 to 50 ℃.When making water in the step (2) in the inventive method, water can be united use separately or with the solvent beyond dewatering.As the solvent beyond dewatering, can use not any those solvents with the dialkyl carbonate reaction.In this case, when water with its with the used identical alcohol of step (1) in the form of solution when using, it is easy that the fractionation by distillation solvent becomes.
As distillating method, can mention the common known distillating method in this area, for example under atmospheric pressure distill, under reduced pressure distill and under superatmospheric pressure, distill.Distillation can-20 ℃ to the temperature of boiling point of dialkyl carbonate and/or alcohol, preferred 50 ℃ are carried out to the temperature of the boiling point of dialkyl carbonate and/or alcohol.Distillation can be undertaken in the presence of another kind of solvent or by extractive distillation.
The dialkyl carbonate that step (1) gained reaction mixture contains also can separate by following method.Add entry and/or extraction solvent in step (1) gained reaction mixture, obtain containing the mixture of oil phase, described oil phase contains dialkyl carbonate, reclaims dialkyl carbonate then from mixture.
Isolating dialkyl carbonate like this can former state be used in the step (4).Select as an alternative, if necessary, be used for step (4) before, dialkyl carbonate can be by the ordinary method purifying.
In step (3), make step (2) gained residual liquid and alcohol (i.e. first kind of alcohol) reaction, generate at least a organometallic compound and water, from organometallic compound, remove then and anhydrate.Step (3) can be undertaken by application WO 03/055840 or WO 04/014840 described method before the inventor.Step (2) gained residual liquid contains metal after separating dialkyl carbonate.Residual liquid generally obtains with the form of transparent liquid.But, in residual liquid, metal exists with solid form sometimes.Even in this case, also can be by the residual liquid synthesis of organometallic compounds in the step (3).
The water that generates in step (3) can for example distill from organometallic compound and remove by a kind of method.
The used first kind of alcohol of step (3) can contain aromatic hydroxy compound and/or carboxylated compound.But, aromatic hydroxy compound and the carboxylated compound total content in the used first kind of alcohol of step (3) preferably 1,000ppm or following, more preferably 100ppm or following.For the amount of controlling aromatic hydroxy compound and carboxylated compound to reach the above-mentioned concrete total content of these compounds, if necessary, first kind of alcohol can be used for step (3) before by conventional purification process purifying, for example distillation purifying.In order to reach the described concrete total content of above-claimed cpd, preferably using boiling point (under atmospheric pressure measure) is that 300 ℃ or lower alcohol are as first kind of alcohol.
When the use polyvalent alcohol is pure as first kind in the step (3), can in step (3), the cross-linking products form with formula (1) or (2) organometallic compound obtain organometallic compound (metal alcoholate or metal virtue alcoholate).Even described cross-linking products also can be with in the present invention.
In step (3), the amount of first kind of alcohol is preferably with respect to 1 to 10,000 times of the stoichiometric quantity of the used organometallic compound amount of step (1), more preferably 2 to 100 times.
The temperature of step (3) reaction is different because of the type of the used alcohol of step (3); But, step (3) reaction is generally carried out under to 300 ℃ in room temperature (20 ℃).
Removing of water can be undertaken by any conventional dewatering that adopt usually this area in the step (3).Removing of water can for example utilize packing to have dehydration tower, distillation or the membrane sepn of solid dewatering agent (for example molecular sieve) to carry out.But, when planning to obtain a large amount of organometallic compound at short notice, preferably, (using the shortcoming of solid dewatering agent to be that the regeneration of solid dewatering agent is trouble) carried out in removing by distillation of water.Distillation can be undertaken by any conventional distillating method, for example distillation, distillation, distillation under superatmospheric pressure, thin film distillation or extractive distillation under reduced pressure under atmospheric pressure.Distillation can be carried out to the temperature of the boiling point of the used first kind of alcohol of step (3) at-20 ℃, preferably carries out to the temperature of the boiling point of first kind of alcohol at 50 ℃.There is no need to go into details, when utilizing pressure-resistant apparatus to distill, distillation can be carried out (described vapour pressure is to measure) under the high temperature that is adopted at high temperature with under the vapour pressure of first kind of alcohol, perhaps can carry out under superatmospheric pressure, and this realizes by introducing rare gas element to pressure-resistant apparatus.When utilizing pressure-resistant apparatus to distill under above-mentioned superatmospheric pressure, distillation temperature is the boiling point from the boiling point of first kind of alcohol under atmospheric pressure measuring to first kind of alcohol measuring under above-mentioned superatmospheric pressure.As described below, in order effectively to distill, can use some material (for example following and water forms the solvent of azeotropic mixture).When the alcohol of boiling point that uses boiling point to be higher than water is pure as first kind, can pass through dephlegmate.When carrying out removing of water by membrane sepn, anhydrate in order to remove effectively, preferably, carry out removing of water by pervaporation.
When carrying out the removing of water in the step (3) by distillation, distillation temperature has no particular limits, if distillation temperature is equal to or less than the boiling point of first kind of alcohol and under this temperature glassware for drinking water vapour pressure is arranged.When planning to finish distillation at short notice, preferably, under the azeotropic temperature of the mixture of water and first kind of alcohol, distill.When water and first kind of alcohol do not form azeotropic mixture, preferably, under the boiling point of water, distill.
And then, even when first kind of alcohol can not form azeotropic mixture with water, also can remove and anhydrate by component distillation, in this distillation, use the solvent that forms azeotropic mixture with water.This method is preferred, because water can be removed under lower temperature.The example that forms the solvent of azeotropic mixture with water comprises unsaturated and saturated hydrocarbon, for example hexane, benzene,toluene,xylene and naphthalene; Ether, phenylmethylether and 1 for example, 4-diox; Halohydrocarbon, for example chloroform.
Consideration for help separating water outlet from azeotropic mixture behind component distillation preferably makes water have the unsaturated or stable hydrocarbon of low solubility therein as the above-mentioned solvent that is used to form azeotropic mixture.When using this solvent, the consumption of this solvent must make can be satisfactorily except that anhydrating by component distillation.The preferred distillation tower that uses carries out component distillation, because can therefore can only carry out component distillation with more a spot of solvent with this solvent recycled to reaction system isolate solvent from azeotropic mixture after in distillation tower.
If necessary, step (3) reaction can be carried out in the presence of rare gas element.By in the used reaction vessel of step (3), introducing rare gas element, can from reaction vessel, remove the water that is present in the vapor phase, so that can promote step (3) reaction sometimes.About rare gas element, have no particular limits, as long as this rare gas element can sharp influence step (3) reaction.The example of this class rare gas element comprises nitrogen, argon gas and helium.Replace rare gas element, can also use organic solvent above-mentioned and water formation azeotropic mixture with gaseous form.
And then, replace rare gas element, also can use carbonic acid gas.Carbonic acid gas is not a rare gas element.But, carbonic acid gas can be used in the step (3), because carbonic acid gas does not have disadvantageous effect.In addition, when in step (3), using carbonic acid gas, can make the organometallic compound and the carbon dioxide reaction that generate by residual liquid and reaction between first kind of alcohol sometimes, the generation dialkyl carbonate.Similarly, can introduce and the first kind of alcohol that alcohol is identical that is used for step (3) reaction, because the alcohol of gaseous form can influence step (3) reaction sharply with gaseous form.Can to the used reaction vessel of step (3), introduce rare gas element from the arbitrary portion of reaction vessel; But preferably, introduce rare gas element from the liquid phase of bottom to reaction vessel of reaction vessel.The amount of introducing rare gas element in reaction vessel can suitably depend on the shape of reaction vessel and the reaction conditions of step (3) reaction.
Type about the used reaction vessel of step (3) has no particular limits, and can use any conventional reaction vessel.Preferably use the wherein bigger reaction vessel of area at the vapor/liquid phases interface of residual liquid.Also preferred stirred vessel with baffle plate or the bubble-plate column of using is as reaction vessel.
By step (3) reaction (just first kind of alcohol and contain reaction between the residual liquid of metallic components), generate at least a organometallic compound and water.This organometallic compound generally is made of at least a organometallic compound of the organometallic compound of free style (1) and (2) representative that selects.
When the generation that confirms water has almost stopped, can stopping step (3).When making the reaction mixture (step (3) gained) that contains organic metallic compound and water when being recycled to step (1), the big existence of water gaging in reaction mixture causes the reduction of dialkyl carbonate productive rate in the step (1) inevitably.Therefore, preferably, remove the water in step (3) the gained reaction mixture as much as possible.
Generally speaking, the water yield of removing in step (3) is 0.01 to 1 times by the water yield of step (3) reaction generation, wherein the water yield of Chan Shenging is calculated under following hypothesis in theory, that is, suppose that the organometallic compound of only being represented by above-mentioned formula (1) (for example metal alcoholate or metal virtue alcoholate) is produced by step (3) reaction.
After step (3) is finished, if necessary, can remove first kind of excessive alcohol.For making step (3) gained reaction mixture be recycled to the consideration that improves the purity of dialkyl carbonate under the situation of step (1), preferably remove first kind of excessive alcohol.But, when in step (1), using the alcohol identical when pure, needn't remove first kind of excessive alcohol, and if necessary as second kind with the used first kind of alcohol of step (3), can be after finish step (3) in reaction mixture an amount of alcohol of adding.And then if necessary, be recovered in the organometallic compound that step (3) is contained in the reaction mixture after finishing, to be used for step (1).
When obtaining organometallic compound (for example metal alcoholate or metal virtue alcoholate) with solid form in step (3), removing of first kind of excessive alcohol can be carried out (wherein removing first kind of alcohol as filtrate) by filtration.On the other hand, when obtaining organometallic compound with liquid form, removing of first kind of excessive alcohol can be undertaken by distillation under reduced pressure, perhaps carries out with the method for first kind of alcohol removing at least a portion and exist with the steam form by wherein introduce rare gas element (as nitrogen) in the used reaction vessel of step (3).When removing of first kind of excessive alcohol undertaken by the method that adopts rare gas element, must use dry gratifying gas as rare gas element.Otherwise organometallic compound (for example metal alcoholate or metal virtue alcoholate) hydrolysis in the presence of the water that rare gas element contained inevitably generates metal oxide and alcohol thus.Therefore, significantly reduction can be recycled to the amount of the organometallic compound of step (1) inevitably, makes step (3) gained reaction mixture be recycled to the productive rate that reduces gained dialkyl carbonate in the step (1) under the situation of step (1) greatly thus.
Remove the organometallic compound that anhydrates and be recycled in the step (1) making therefrom, organometallic compound can be recycled to step (1) at it and cool off before or heat.The recirculation of organometallic compound can be undertaken by continuous or batch mode.If necessary, except the organometallic compound that in step (3), is reclaimed, can use fresh organometallic compound.
In step (4), make the dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.Particularly, in step (4), the dialkyl carbonate that use is separated in step (2) (by following formula (24) representative) is as raw material, make its with as the aromatic hydroxy compound of the reagent aromatic hydroxy compound of following formula (3) representative (for example by) reaction, obtain aromatic carbonate thus.Generally speaking, step (4) gained aromatic carbonate comprises at least a being selected from by the carbonate alkyl aryl ester of following formula (27) representative with by the aromatic carbonate of the diaryl carbonate of following formula (28) representative.In formula (27) carbonate alkyl aryl ester and formula (28) diaryl carbonate each can obtain with the form of mixtures of two or more different aromatic carbonates.
With
R wherein
21Representative and the contained alkyl R of following formula (24) dialkyl carbonate that is used as raw material
15Or R
16Identical alkyl, Ar
1, Ar
2And Ar
3In each representative and the identical aromatic group (for example R group in the following formula (3)) of the contained aromatic group of aromatic hydroxy compound that is used as reagent.
Example by the carbonate alkyl aryl ester of following formula (27) representative comprises the carbonic acid methyl. phenylester, the carbonic acid ethyl. phenylester, the carbonic acid propyl group. phenylester (and isomer), the carbonic acid allyl group. phenylester, the carbonic acid butyl. phenylester (and isomer), the carbonic acid amyl group. phenylester (and isomer), the carbonic acid hexyl. phenylester (and isomer), the carbonic acid heptyl. phenylester (and isomer), the carbonic acid octyl group. tolyl ester (and isomer), the carbonic acid nonyl. ethyl phenyl ester (and isomer), the carbonic acid decyl. butyl phenyl ester (and isomer), the carbonic acid methyl. tolyl ester (and isomer), the carbonic acid ethyl. tolyl ester (and isomer), the carbonic acid propyl group. tolyl ester (and isomer), the carbonic acid butyl. tolyl ester (and isomer), the carbonic acid allyl group. tolyl ester (and isomer), the carbonic acid methyl. xylyl ester (and isomer), the carbonic acid methyl. trimethylphenyl ester (and isomer), the carbonic acid methyl. chloro-phenyl-ester (and isomer), the carbonic acid methyl. nitrophenyl ester (and isomer), the carbonic acid methyl. p-methoxy-phenyl ester (and isomer), the carbonic acid methyl. cumyl ester (and isomer), the carbonic acid methyl. naphthyl ester (and isomer), the carbonic acid methyl. pyridyl ester (and isomer), the carbonic acid ethyl. cumyl ester (and isomer), the carbonic acid methyl. benzoyloxy phenyl ester (and isomer), the carbonic acid ethyl. xylyl ester (and isomer) and carbonic acid benzyl. the xylyl ester.
Example by the diaryl carbonate of following formula (28) representative comprises diphenyl carbonate, carboxylol ester (and isomer), carbonic acid two-xylyl ester (and isomer), the carbonic acid tolyl. phenylester (and isomer), the carboxylol base. phenylester (and isomer), the carboxylol base. tolyl ester (and isomer), carbonic acid dinaphthyl ester, carbonic acid diethyl phenyl ester (and isomer), carbonic acid two (propyl group phenyl) ester (and isomer), carbonic acid two (butyl phenyl) ester, carbonic acid two (trimethylphenyl) ester (and isomer), carbonic acid two (p-methoxy-phenyl) ester (and isomer), carbonic acid two (chloro-phenyl-) ester (and isomer) and carbonic acid two (nitrophenyl) ester.
About the method for producing carbonate alkyl aryl ester and/or diaryl carbonate, known the wide variety of conventional method by dialkyl carbonate and aromatic hydroxy compound.In the present invention, the production of carbonate alkyl aryl ester and/or diaryl carbonate can be undertaken by any this class ordinary method.
In the present invention, following formula (9) reaction of carrying out in step (4) is the transesterification reaction between dialkyl carbonate and the aromatic hydroxy compound.This reaction is a kind of balanced reaction, therefore in order to make reaction progress (balance of reaction is moved to the direction that generates required product), preferably, takes out the alcohol of supervening when reacting from reaction system.For the consideration of taking out the alcohol of supervening effectively, preferably, the boiling point of the used aromatic hydroxy compound of step (4) is higher than the boiling point of the used alcohol of step (3) (i.e. first kind of alcohol).Especially when repeating at least one time, the circulation of step (1) to (4) (that is to say, the circulation of step (1) to (4) carries out at least twice), preferably, the boiling point of each in first kind of alcohol (being used in the step (3)), second kind of alcohol (being used in the step (1)) and the third alcohol (being used in the step (2)) is lower than the boiling point of the used aromatic hydroxy compound of step (4).Particularly, preferably, the boiling point of each in first kind of alcohol, second kind of pure and mild the third alcohol is than low at least 2 ℃ of the boiling point of aromatic hydroxy compound.And then for the consideration of taking out easily the alcohol of supervening in step (4), more preferably, the boiling point of each in first kind of alcohol, second kind of pure and mild the third alcohol is than low at least 10 ℃ of the boiling point of aromatic hydroxy compound.
About first kind of alcohol that step (3) is used, preferably, the boiling point of first kind of alcohol is higher than the boiling point of water.Be higher than in the alcohol of boiling point of water at this class boiling point, preferred 1-butanols, 2-methyl isophthalic acid-propyl alcohol, have straight or branched C
5-C
12The alkyl alcohol of alkyl, has straight or branched C
4-C
12The alkenyl alcohol of thiazolinyl, cycloalkyl alcohol and aralkyl alcohol.And then for take out the alcohol of supervening so that step (4) is reacted the consideration of progress from reaction vessel in step (4), more preferably, the boiling point of the used first kind of alcohol of step (3) is lower than the boiling point of the used aromatic hydroxy compound of step (4).In step (4), from reaction vessel, take out the alcohol of supervening with gaseous form, and from reaction vessel, take out carbonate alkyl aryl ester and/or the diaryl carbonate that is produced with liquid form.Therefore, preferably, the used dialkyl carbonate of step (4) is to be higher than the boiling point of water from boiling point but to be lower than the ester that the alcohol of the boiling point of aromatic hydroxy compound obtains, and the boiling point of dialkyl carbonate is lower than the boiling point of dialkyl carbonate and the boiling point of diaryl carbonate.
And then, with top identical explanation also is applicable to the situation of the used second kind of alcohol of step (1) about the used first kind of alcohol of step (3).Particularly, preferably, but the boiling point of second kind of alcohol is higher than the boiling point of water is lower than the boiling point of the used aromatic hydroxy compound of step (4).The preferred embodiment of second kind of alcohol comprises the alcohol with straight or branched alkyl, for example propyl carbinol, 2-methyl isophthalic acid-propyl alcohol, amylalcohol (and isomer), hexanol (and isomer), enanthol (and isomer), octanol (and isomer), nonyl alcohol (and isomer), decyl alcohol (and isomer), dodecanol (and isomer); And the alcohol with cycloalkyl, for example cyclobutanol, cyclopentanol and hexalin.And then, when carrying out the removing of water in the step (3) by distillation, when perhaps taking out supervene pure from reaction vessel when carrying out step (4) reaction, preferably, the used second kind of alcohol of step (1) is selected from 1-butanols, 2-methyl isophthalic acid-propyl alcohol, straight or branched C
5-C
8Alkyl alcohol and C
5-C
8Alicyclic alcohol.The most preferably example of second kind of alcohol comprises 1-butanols, 2-methyl isophthalic acid-propyl alcohol and straight or branched C
5-C
6Alkyl alcohol.
About above-mentioned alcohol, dialkyl carbonate and aromatic hydroxy compound, most preferably, first kind of alcohol, second kind of alcohol, the third alcohol, all be the primary alconol that is selected from 1-butanols, 2-methyl isophthalic acid-propyl alcohol, amylalcohol (and isomer) and hexanol (and isomer), and aromatic hydroxy compound is selected from phenol and cresols corresponding to alcohol by the pure and mild alkoxyl group corresponding to dialkyl carbonate of the alkoxyl group of the organometallic compound (having metal-carbon-oxygen key) of following formula (1) or (2) representative.
In step (4), preferably, the consumption of aromatic hydroxy compound is 0.1 to 10,000 times with respect to the stoichiometric quantity of dialkyl carbonate amount.The consumption of aromatic hydroxy compound is big more, and the turnout of aromatic carbonate is just big more.But, when the amount of aromatic hydroxy compound is too big, must use large-scale reaction vessel.And then, because the reaction that great majority occur in the step (4) is balanced reaction (for example referring to following formula (9)), therefore use the shortcoming of too a large amount of aromatic hydroxy compounds to be: the aromatic carbonate of producing in order to reclaim, must use the large distillation tower.Therefore in step (4), the amount of aromatic hydroxy compound more preferably is 0.5 to 100 times with respect to the stoichiometric quantity of dialkyl carbonate amount, most preferably 0.5 to 10 times.
In step (4), dialkyl carbonate and aromatic hydroxy compound are sent in the reaction vessel.If necessary, also can use catalyzer.This impurity in the reaction system of step (4), can have impurity, as long as can influence step (4) reaction sharply.
Can contain alcohol, carbonate alkyl aryl ester and diaryl carbonate as the dialkyl carbonate of step (4) raw material and each in the aromatic hydroxy compound, they are the products that generate in step (4).But, the reaction of being produced carbonate alkyl aryl ester by dialkyl carbonate and aromatic hydroxy compound is a kind of balanced reaction (being reversible reaction) (referring to following formula (9)), therefore, when the amount of above-mentioned product in raw material is big, the danger that exists feed stock conversion to reduce.The ratio of aromatic hydroxy compound and the quantity of dialkyl carbonate is different because of the type of catalyst system therefor and consumption and reaction conditions; But, this quantity is pressed the molar ratio computing of aromatic hydroxy compound and dialkyl carbonate than preferably 0.01 to 1,000.Method as adding catalyzer can preferably adopt ordinary method.When the circulation by repeating step (1) to (4) or step (1) when the production of aromatic carbonate is carried out in the circulation of (5), can make step (4) catalyst system therefor recirculation.The live catalyst that can in step (4), add in this case, magnitude of recruitment.
The time of step (4) reaction is different because of the type and the internal structure of reaction conditions and reaction vessel.But, this reaction times generally is 0.001 to 50 hour, preferred 0.01 to 10 hour, and more preferably 0.05 to 5 hour.Temperature of reaction (being the temperature in the reaction vessel) is because of different as the type of the dialkyl carbonate of raw material and aromatic hydroxy compound.But, this temperature of reaction generally is 50 to 350 ℃, preferred 100 to 280 ℃.Reaction pressure can be decompression, normal atmosphere or superatmospheric pressure, and this depends on as the type of the dialkyl carbonate of raw material and aromatic hydroxy compound and temperature of reaction.But, this reaction pressure generally is 10Pa to 20MPa.
In step (4), must not use solvent.But, in order to help the operation in the step (4), can use inert solvent.The example of inert solvent comprises ether, aliphatic hydrocrbon, aromatic hydrocarbon, halogenated aliphatic hydrocarbon and halogenated aromatic hydrocarbons.And then step (4) reaction can be in that reaction be in the presence of the inert gasses and carries out to step (4).The lower boiling organic compound that the example of this class rare gas element comprises nitrogen, helium, argon gas and reaction is the inert gasification to step (4).When utilizing the continuous multi-stage distillation tower to carry out step (4), can to distillation tower, introduce the low melting point organic compound of above-mentioned rare gas element or gasification from the bottom of distillation tower for promoting distillation to remove the purpose of low-boiling by-products.
After step (4) is finished, by ordinary method isolation of aromatic carbonic ether from dialkyl carbonate, aromatic hydroxy compound, the pure and mild catalyzer (if any) supervened, reclaim aromatic carbonate (as mentioned above, in step (4), can use catalyzer) thus.Each following formula (9) that carries out in step (4) and (10) reaction are transesterification reactions.By these transesterification reactions, obtain carbonate alkyl aryl ester and diaryl carbonate by dialkyl carbonate.But, about each formula (9) and (10) transesterification reaction, the direction of the original system of balanced deflection of reaction, the speed of reaction is lower.Therefore, in order to improve the method for utilizing above-mentioned transesterification reaction to produce aromatic carbonate, Several Methods has been proposed.Can preferably adopt this class to improve one's methods in the present invention.
About catalyst for ester exchange reaction (just promoting the catalyzer of following formula (9) and (10) transesterification reaction), its consumption is different because of the type of type, carbonic ether and the aromatic hydroxy compound of the type of catalyzer, reaction vessel and consumption and reaction conditions (for example temperature of reaction and reaction pressure).But, the amount of catalyst for ester exchange reaction generally is 0.0001 to 50 weight % based on the dialkyl carbonate that is used as raw material and the gross weight of aromatic hydroxy compound.When using catalyst for ester exchange reaction with solid form, preferably, the amount of catalyzer is 0.01 to 75 volume % based on the internal volume of empty reaction vessel.
As catalyst for ester exchange reaction, a large amount of known containing metal catalyzer are arranged.Can use the catalyst for ester exchange reaction of this class routine arbitrarily in the present invention.The example of catalyst for ester exchange reaction comprises Lewis acid (for example transition metal halide) and generates lewis acidic compound (referring to not examining the clear 51-105032 of Japanese Patent Application Publication specification sheets No., clear 56-123948 and clear 56-123949 (corresponding to not examining Deutsches Reichs-Patent ublic specification of application No.2528412, English Patent No.1499530 and U.S. Patent No. 4,182,726)); Tin compound, for example organotin alcoholate and organotin oxides are (referring to not examining the clear 54-48733 of Japanese Patent Application Publication specification sheets No. (corresponding to not examining Deutsches Reichs-Patent ublic specification of application No.2736062), clear 54-63023, clear 60-169444 (corresponding to U.S. Patent No. 4,554,110), clear 60-169445 is (corresponding to U.S. Patent No. 4,552,704), clear 62-277345 peace 1-265063); The salt of basic metal or alkaline-earth metal and alcoholate (referring to not examining the clear 57-176932 of Japanese Patent Application Publication specification sheets No.); Lead compound (referring to not examining the clear 57-176932 of Japanese Patent Application Publication specification sheets No.); The title complex of metal, for example title complex of copper, iron or zirconium (referring to not examining the clear 57-183745 of Japanese Patent Application Publication specification sheets No.); Titanic acid ester (referring to not examining the clear 58-185536 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,410,464)); The mixture of Lewis acid and protonic acid (referring to not examining the clear 60-173016 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,609,501)); The compound of Sc, Mo, Mn, Bi or Te (referring to not examining the flat 1-265064 of Japanese Patent Application Publication specification sheets No.); And ironic acetate (referring to not examining the clear 61-172852 of Japanese Patent Application Publication specification sheets No.).
Can unite with catalyst for ester exchange reaction and use disproportionation reaction catalyzer (just promoting following formula (11) catalyst for reaction).A large amount of disproportionation reaction catalyzers also are known.The example of disproportionation reaction catalyzer comprises Lewis acid and produces lewis acidic transistion metal compound (referring to not examining the clear 51-75044 of Japanese Patent Application Publication specification sheets No. (corresponding to not examining Deutsches Reichs-Patent ublic specification of application No.2552907 and U.S. Patent No. 4,045,464)); Polymerization tin compound (referring to not examining the clear 60-169444 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,554,110)); By formula R-X (=O) compound of OH representative, wherein X is Sn or Ti, R is monovalence alkyl (referring to examining the clear 60-169445 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,552,704)); The mixture of Lewis acid and protonic acid (referring to not examining the clear 60-173016 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,609,501)); Lead compound (referring to not examining the flat 1-93560 of Japanese Patent Application Publication specification sheets No.); The compound of titanium or zirconium (referring to not examining the flat 1-265062 of Japanese Patent Application Publication specification sheets No.); Tin compound (referring to not examining the flat 1-265063 of Japanese Patent Application Publication specification sheets No.); Compound (referring to not examining the flat 1-265064 of Japanese Patent Application Publication specification sheets No.) with Sc, Mo, Mn, Bi or Te.
About the reaction of in the inventive method step (4), carrying out, attempted revising reaction pattern, molecular balance is moved to the direction that produces required product as far as possible, improve the productive rate of aromatic carbonate thus.For example, a kind of like this method has been proposed, wherein the methyl alcohol of being supervened by the reaction of methylcarbonate and phenol is removed (referring to examining the clear 54-48732 of Japanese Patent Application Publication specification sheets No. (corresponding to examining Deutsches Reichs-Patent ublic specification of application No.736063 and U.S. Patent No. 4 with the azeotropic mixture form distillation that itself and azeotrope form agent, 252,737) and clear 61-291545); A kind of like this method, wherein the methyl alcohol of being supervened by the reaction of methylcarbonate and phenol is removed (referring to examining the clear 58-185536 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 410,464)) by it being adsorbed onto on the molecular sieve.
And then, a kind of like this method has also been proposed, wherein the alcohol of being supervened by the transesterification reaction reaction vessel distillation that utilizes its top to be connected with distillation tower is removed (referring to examining the clear 56-123948 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,182,726) work example, do not examine the work example of the clear 56-25138 of Japanese Patent Application Publication specification sheets No., do not examine the clear 60-169444 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,554,110) work example, do not examine the clear 60-169445 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,552,704) work example, do not examine the clear 60-173016 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,609,501) work example, do not examine the work example of the clear 61-172852 of Japanese Patent Application Publication specification sheets No., examine the work example and the work example of not examining the clear 62-277345 of Japanese Patent Application Publication specification sheets No. of the clear 61-291545 of Japanese Patent Application Publication specification sheets No.).
And, also known a kind of like this method, wherein dialkyl carbonate and aromatic hydroxy compound are sent in the multistage distillation tower continuously, in this distillation tower, to react, wherein when reacting continuously, contain the low boiling mixture of the alcohol of supervening and the continuous reaction mixture (referring to the careful flat 3-291257 of Japanese Patent Application Publication specification sheets No.) that contains the carbonate alkyl aryl ester of producing to some extent that takes out from the continuous taking-up in the top of distillation tower from the distillation tower bottom by distillation.By any aforesaid method, can carry out the continuous production of aromatic carbonate effectively.
Other example of the method for continuous production aromatic carbonate comprises the method (referring to not examining the flat 6-41022 of Japanese Patent Application Publication specification sheets No., flat 6-157424 peace 6-184058) of wherein carrying out transesterification reaction in the tower reaction vessel in the presence of catalyzer; Wherein polyphone connects the method (not examining the flat 6-234707 peace of Japanese Patent Application Publication specification sheets No. 6-263694) of a plurality of reaction vessels; Utilize the method (not examining the flat 6-298700 of Japanese Patent Application Publication specification sheets No.) of bubble column reaction vessel; With the method for utilizing vertical reaction vessel (not examining the flat 6-345697 of Japanese Patent Application Publication specification sheets No.).
In the industrial-scale production of aromatic carbonate, also attempted producing long-term and stably.For example, in preventing the trial of catalyst deposit in distillation tower, do not examine the flat 6-157410 of Japanese Patent Application Publication specification sheets No. and propose a kind of like this method, wherein be connected with in the process of reaction vessel by dialkyl carbonate and aromatic hydroxy compound production aromatic carbonate of distillation tower in utilization, from distillation tower, take out the fatty alcohol of supervening, so that fatty alcohol concentration in the reaction mixture in tower is suppressed to 2 weight % or lower.This part patent documentation is described to, and aforesaid method can stably be realized the continuous production of aromatic carbonate.And then, preventing in the trial of catalyst deposit in distillation tower for the purpose of long-time stably manufactured aromatic carbonate, the open flat 9-11049 of No. discloses a kind of like this method before the Japanese patent application examination, wherein the amount of aromatic hydroxy compound in containing the reaction mixture of catalyzer suppressed to 2 or below, by the weight ratio of aromatic hydroxy compound and catalyzer institute containing metal.
Be known that and producing in the process of aromatic carbonate, supervene and have high boiling compound by dialkyl carbonate and aromatic hydroxy compound.For example, the careful clear 61-172852 of Japanese Patent Application Publication specification sheets No. has described and has produced in the process of diphenyl carbonate by the transesterification reaction of methylcarbonate and phenol, supervene the impurity of boiling point near the boiling point of diphenyl carbonate, this impurity mixes with the diphenyl carbonate of being produced, and causes that thus variable color takes place the final product (for example polycarbonate) that utilizes diphenyl carbonate to obtain.As the example of boiling point near the impurity of the boiling point of diaryl carbonate (for example diphenyl carbonate), can mention the aryloxycarbonyl hydroxy arene, it is the isomer of diaryl carbonate, and produces (at the above-mentioned example of not describing this impurity among the clear 61-172852 of Japanese Patent Application Publication specification sheets No. of not examining) by the Fries rearrangement reaction of diaryl carbonate.When using diphenyl carbonate as diaryl carbonate, above-mentioned aryloxycarbonyl hydroxy arene is the Whitfield's ointment phenylester, and it has high boiling point, and is higher 4 to 5 ℃ than the boiling point of diphenyl carbonate.When carrying out producing the reaction of aromatic carbonate for a long time by dialkyl carbonate and aromatic hydroxy compound, above-mentioned higher-boiling compound is accumulated in the reaction system gradually, so that the amount of the higher-boiling compound that contains in the aromatic carbonate of being produced increases, and reduces the purity of aromatic carbonate thus.And then along with the amount increase of the contained higher-boiling compound of reaction mixture, the elevation of boiling point of reaction mixture causes further promotion to supervene the problem of higher-boiling compound thus.
But on the other hand, by examining the described method of the flat 11-92429 of Japanese Patent Application Publication specification sheets No., the aromatic carbonate of production high purity stably and need not a large amount of catalyzer.
The specific examples of catalyst for ester exchange reaction comprises following compounds:
＜lead compound〉lead oxides, for example PbO, PbO
2And Pb
3O
4Plumbous sulfide, for example PbS and Pb
2S; Plumbous oxyhydroxide, for example Pb (OH)
2And Pb
2O
2(OH)
2Plumbite, for example Na
2PbO
2, K
2PbO
2, NaHPbO
2And KHPbO
2Plumbate, for example Na
2PbO
3, Na
2H
2PbO
4, K
2PbO
3, K
2[Pb (OH)
6], K
4PbO
4, Ca
2PbO
4And CaPbO
3Plumbous carbonate and basic salt, for example PbCO
3And 2PbCO
3.Pb (OH)
2The carbonate and the subsalt of plumbous organic acid salt and plumbous organic acid salt, for example Pb (OCOCH
3)
2, Pb (OCOCH
3)
4, Pb (OCOCH
3)
2.PbO.3H
2O; Organo-lead compound, for example Bu
4Pb, Ph
4Pb, Bu
3PbCl, Ph
3PbBr, Ph
3Pb (or Ph
6Pb
2), Bu
3PbOH and Ph
3PbO (wherein Bu represents butyl, and Ph represents phenyl); Plumbous alcoholate and plumbous fragrant alcoholate, for example Pb (OCH
3)
2, (CH
3O) Pb (OPh) and Pb (OPh)
2Lead alloy, for example Pb-Na, Pb-Ca, Pb-Ba, Pb-Sn and Pb-Sb; Lead minerals, for example lead glance and zink sulphide; And the hydrated product of these lead compounds;
＜copper family metallic compound〉copper family metal-salt and title complex, for example CuCl, CuCl
2, CuBr, CuBr
2, CuI, CuI
2, Cu (OAc)
2, Cu (acac)
2, cupric oleate, Bu
2Cu, (CH
3O)
2Cu, AgNO
3, AgBr, silver trinitrophenolate, AgC
6H
6ClO
4, Ag (bullvalene)
3NO
3, [AuC ≡ C-C (CH
3)
3]
n[Cu (C
7H
8) Cl]
4(wherein acac represents the methyl ethyl diketone chelating ligand);
＜alkali metal complex〉alkali metal complex, for example Li (acac) and LiN (C
4H
9)
2
＜Zn complex〉Zn complex, for example Zn (acac)
2
＜cadmium complex〉cadmium complex, for example Cd (acac)
2
＜iron family metal compound〉iron family metal title complex, for example Fe (C
10H
8) (CO)
5, Fe (CO)
5, Fe (C
4H
6) (CO)
3, Co (_)
2(PEt
2Ph)
2, CoC
5F
5(CO)
7, Ni-π-C
5H
5NO and ferrocene;
＜zirconium complex〉zirconium complex, for example Zr (acac)
4And zirconocene;
＜lewis acid compound〉Lewis acid and generation lewis acidic transistion metal compound, for example AlX
3, TiX
3, TiX
4, VOX
3, VX
5, ZnX
2, FeX
3And SnX
4(wherein X represents halogen atom, acetoxyl group, alkoxyl group or aryloxy); With
＜organo-tin compound〉organo-tin compound, for example (CH
3)
3SnOCOCH
3, (C
2H
5)
3SnOCOC
6H
5, Bu
3SnOCOCH
3, Ph
3SnOCOCH
3, Bu
2Sn (OCOCH
3)
2, Bu
2Sn (OCOC
11H
23)
2, Ph
3SnOCH
3, (C
2H
5)
3SnOPh, Bu
2Sn (OCH
3)
2, Bu
2Sn (OC
2H
5)
2, Bu
2Sn (OPh)
2, Ph
2Sn (OCH
3)
2, (C
2H
5)
3SnOH, Ph
3SnOH, Bu
2SnO, (C
8H
17)
2SnO, Bu
2SnCl
2And BuSnO (OH).
There is no need to go into details, each above-mentioned catalyst for ester exchange reaction can use with its form with the reaction product that is present in the organic compound in the reaction system, and wherein said organic compound for example is alcohol, aromatic hydroxy compound, carbonate alkyl aryl ester, diaryl carbonate or dialkyl carbonate.And then, each above-mentioned catalyst for ester exchange reaction can be before it uses with step (4) raw materials used or step (4) product heat-treat.
Preferably, catalyst for ester exchange reaction has high-dissolvability in reaction mixture under reaction conditions.The preferred embodiment of catalyst for ester exchange reaction comprises PbO, Pb (OH)
2And Pb (OPh)
2TiCl
4And Ti (OPh)
4SnCl
4And Sn (OPh)
4Bu
2SnO and Bu
2Sn (OPh)
2FeCl
3, Fe (OH)
3And Fe (OPh)
3With the compound that above-claimed cpd is obtained with phenol or reaction mixture processing.
As mentioned above, in step (4), produce aromatic carbonate by the transesterification reaction (balanced reaction) of dialkyl carbonate and aromatic hydroxy compound.The amount of the aromatic carbonate of producing in order to increase preferably, is taken out the alcohol of supervening from reaction system when reacting.And then the disproportionation reaction of carbonate alkyl aryl ester (wherein producing the reaction of diaryl carbonate and dialkyl carbonate) also is balanced reaction (referring to following formula (11)).Therefore, when planning to increase the amount of diaryl carbonate in the aromatic carbonate of being produced, a kind of like this method of preferred employing is wherein taken out one of dialkyl carbonate and diaryl carbonate (all being produced by disproportionation reaction separately) from reaction system when carrying out disproportionation reaction.
In step (4), preferably, the selection of the aryl of the alkyl of the dialkyl carbonate of being produced and the aromatic carbonate of being produced should make the boiling point of dialkyl carbonate be lower than the boiling point of aromatic carbonate, further preferably, when reacting, from reaction system, take out the dialkyl carbonate of being produced.
As mentioned above, in step (4), reaction can not only carried out in the presence of catalyst for ester exchange reaction but also the disproportionation reaction catalyzer (promoting following formula (11) catalyst for reaction).The example of disproportionation reaction catalyzer comprises Lewis acid and produces lewis acidic transistion metal compound (referring to not examining the clear 51-75044 of Japanese Patent Application Publication specification sheets No. (corresponding to not examining Deutsches Reichs-Patent ublic specification of application No.2552907 and U.S. Patent No. 4,045,464)); Polymerization tin compound (referring to not examining the clear 60-169444 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,554,110)); By the formula R-X (=O) compound (wherein X is Sn or Ti, and R is the monovalence alkyl) of OH representative (referring to examining the clear 60-169445 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,552,704)); The mixture of Lewis acid and protonic acid (referring to not examining the clear 60-173016 of Japanese Patent Application Publication specification sheets No. (corresponding to U.S. Patent No. 4,609,501)); Lead compound (referring to not examining the flat 1-93560 of Japanese Patent Application Publication specification sheets No.); The compound of titanium or zirconium (referring to not examining the flat 1-265062 of Japanese Patent Application Publication specification sheets No.); Tin compound (referring to not examining the flat 1-265063 of Japanese Patent Application Publication specification sheets No.); Compound (referring to not examining the flat 1-265064 of Japanese Patent Application Publication specification sheets No.) with Sc, Mo, Mn, Bi or Te.
The specific examples of disproportionation reaction catalyzer comprises and the listed identical catalyzer of top specific examples about catalyst for ester exchange reaction.
There is no need to go into details, each above-mentioned disproportionation reaction catalyzer can use with its form with the reaction product that is present in the organic compound in the reaction system, and wherein said organic compound for example is alcohol, aromatic hydroxy compound, carbonate alkyl aryl ester, diaryl carbonate or dialkyl carbonate.And then, each above-mentioned disproportionation reaction catalyzer can be before it uses with step (4) raw materials used or step (4) product heat-treat.
Preferably, disproportionation reaction catalyzer has high-dissolvability in reaction mixture under reaction conditions.The preferred embodiment of disproportionation reaction catalyzer comprises with top about the identical catalyzer of the listed preferred embodiment of catalyst for ester exchange reaction.
After step (4) is finished,, reclaim aromatic carbonate thus by ordinary method isolation of aromatic carbonic ether from catalyzer, aromatic hydroxy compound and alcohol.
Type about the used reaction vessel of step (4) has no particular limits, and can use the reaction vessel of any conventional.The example of popular response container comprises stirred vessel, multistage stirred vessel and continuous multi-stage distillation tower.These reaction vessels can separately or be united use.Utilize at least a above-mentioned reaction vessel, can carry out step (4) in mode in batches or continuously.To the consideration that the direction that generates required product moves effectively, preferably utilize the multistage distillation tower for molecular balance.More preferably, utilize the multistage distillation tower to carry out step (4) continuously.
About the multistage distillation tower, have no particular limits, as long as it is to have two or more theoretical stages and distillation tower that can continuous still battery.As this multistage distillation tower, can utilize common usefulness any conventional multistage distillation tower in the art.The example of this class multistage distillation tower comprises the tray column that utilizes tower tray, and described tower tray for example is bubble cap disc, screen tray, valve tray or counter-current tray; With the filled-type tower that is filled with any various fillers, described filler for example is Raschig ring, Lessing ring, Pall ring, Berl saddle packing, Interlox saddle packing, Dixon filler, MeMahon packing, Heli-Pack packing, sumbul oil and ripple packing.And then, also can preferably utilize the mixed type of tray column and packed tower, it comprises plate part and fills Packed part.
When utilizing the multistage distillation tower to carry out by dialkyl carbonate and aromatic hydroxy compound production aromatic carbonate continuously in step (4), this production for example is performed as follows.To send into continuously in the multistage distillation tower as the dialkyl carbonate of raw material with as the aromatic hydroxy compound of reagent, carrying out transesterification reaction between the two in mutually in liquid phase or in solution-air in the presence of the containing metal catalyzer, produce aromatic carbonate thus, and supervene alcohol, wherein take out the high boiling mixture that contains the aromatic carbonate of producing to some extent, take out the low boiling mixture that contains by-product alcohol by distillation continuously from distillation tower top with gaseous form simultaneously from the distillation tower bottom with liquid form.
In step (5), make step (4) gained carbonate alkyl aryl ester carry out disproportionation reaction, produce dialkyl carbonate and diaryl carbonate (referring to following formula (11)) thus.(as mentioned above, in step (4), in the presence of disproportionation reaction catalyzer, not only can carry out above-mentioned transesterification reaction (referring to following formula (9) and (10)), but also can carry out disproportionation reaction.) in step (4) and (5) each can carry out with continuous or batch mode.As mentioned above, in step (4), produce diaryl carbonate with carbonate alkyl aryl ester sometimes.Even in this case, also can after step (4), carry out step (5).
As mentioned above, in step (4), produce carbonate alkyl aryl ester (this transesterification reaction is balanced reaction) by the transesterification reaction between dialkyl carbonate and the aromatic hydroxy compound.For the balance that makes transesterification reaction moves to the direction that generates required product, preferably when carrying out transesterification reaction, from reaction system, take out the alcohol of supervening.Disproportionation reaction in the step (5) also is balanced reaction.Therefore, for the balance that makes disproportionation reaction moves to the direction that generates required product, preferably when carrying out disproportionation reaction, from reaction system, take out one of dialkyl carbonate and diaryl carbonate (they produce in disproportionation reaction).
In step (5), preferably, the selection of the aryl of the alkoxyl group of the dialkyl carbonate of being produced and the diaryl carbonate of being produced should make the boiling point of dialkyl carbonate be lower than the boiling point of diaryl carbonate, further preferably, when carrying out disproportionation reaction, from reaction system, take out the dialkyl carbonate of being produced.More preferably, when taking out the dialkyl carbonate of supervening, take out the diaryl carbonate of being produced with liquid form with gaseous form.Can make the dialkyl carbonate that is taken out be recycled to step (2).In some cases, dialkyl carbonate is produced in step (4).And in this case, can reclaim dialkyl carbonate, and be recirculated to step (4).The amount of the diaryl carbonate of producing in order to increase preferably, makes the dialkyl carbonate that is taken out be recycled to step (4).
In step (5), reaction can be carried out in the presence of disproportionation reaction catalyzer.The example of the used disproportionation reaction catalyzer of step (5) comprises the used disproportionation reaction catalyzer of step (4) that exemplifies above.
There is no need to go into details, each above-mentioned disproportionation reaction catalyzer can use with its form with the reaction product that is present in the organic compound in the reaction system, and wherein said organic compound for example is alcohol, aromatic hydroxy compound, carbonate alkyl aryl ester, diaryl carbonate or dialkyl carbonate.And then each above-mentioned disproportionation reaction catalyzer can be used for step (5) at it and use raw materials used or step (5) product of step (5) to heat-treat before.
Method as adding catalyzer can preferably adopt any conventional method.When step (4) is carried out step (5) afterwards, catalyzer (being used in the step (4)) can former state be used in the step (5).
The example of the used carbonate alkyl aryl ester of step (5) comprises the carbonic acid methyl. phenylester, the carbonic acid ethyl. phenylester, the carbonic acid propyl group. phenylester (and isomer), the carbonic acid allyl group. phenylester, the carbonic acid butyl. phenylester (and isomer), the carbonic acid amyl group. phenylester (and isomer), the carbonic acid hexyl. phenylester (and isomer), the carbonic acid heptyl. phenylester (and isomer), the carbonic acid octyl group. tolyl ester (and isomer), the carbonic acid nonyl. ethyl phenyl ester (and isomer), the carbonic acid decyl. butyl phenyl ester (and isomer), the carbonic acid methyl. tolyl ester (and isomer), the carbonic acid ethyl. tolyl ester (and isomer), the carbonic acid propyl group. tolyl ester (and isomer), the carbonic acid butyl. tolyl ester (and isomer), the carbonic acid allyl group. tolyl ester (and isomer), the carbonic acid methyl. xylyl ester (and isomer), the carbonic acid methyl. trimethylphenyl ester (and isomer), the carbonic acid methyl. chloro-phenyl-ester (and isomer), the carbonic acid methyl. nitrophenyl ester (and isomer), the carbonic acid methyl. p-methoxy-phenyl ester (and isomer), the carbonic acid methyl. cumyl ester (and isomer), the carbonic acid methyl. naphthyl ester (and isomer), the carbonic acid methyl. pyridyl ester (and isomer), the carbonic acid ethyl. cumyl ester (and isomer), the carbonic acid methyl. benzoyloxy phenyl ester (and isomer), the carbonic acid ethyl. xylyl ester (and isomer) and carbonic acid benzyl. the xylyl ester.These carbonate alkyl aryl esters can separately or be united use.
In these carbonate alkyl aryl esters, the preferred carbonate alkyl aryl ester that uses should make: be higher than the boiling point of water and be lower than the boiling point of the used aromatic hydroxy compound of step (4) corresponding to the boiling point of the alcohol of the alkoxyl group of carbonate alkyl aryl ester.The specific examples of this class alcohol comprises 1-butanols, 2-methyl isophthalic acid-propyl alcohol, has straight or branched C
5-C
12The alkyl alcohol of alkyl, has straight or branched C
4-C
12The alkenyl alcohol of thiazolinyl, cycloalkyl alcohol and aralkyl alcohol.For for the balance that makes disproportionation reaction moves and the consideration of taking out the dialkyl carbonate of producing in step (5) to the direction that generates required product, more preferably use boiling point to be lower than the carbonate alkyl aryl ester of the boiling point of the diaryl carbonate of production in step (5).In order to obtain this carbonate alkyl aryl ester, most preferably, first kind of alcohol, second kind of alcohol, the third alcohol, be the primary alconol that is selected from 1-butanols, 2-methyl isophthalic acid-propyl alcohol, amylalcohol (and isomer) and hexanol (and isomer), and aromatic hydroxy compound is phenol or cresols corresponding to pure and mild each corresponding in the alcohol of the contained alkoxyl group of dialkyl carbonate of following formula (1) and the contained alkoxyl group of (2) organometallic compound.
In step (5), use carbonate alkyl aryl ester as raw material.If necessary, also can use disproportionation reaction catalyzer.This impurity in the reaction system of step (5), can have impurity, as long as can influence disproportionation reaction sharply.
The amount of the used disproportionation reaction catalyzer of step (5) is because of the type of the type of catalyzer, used reaction vessel, different as the type of the carbonate alkyl aryl ester of raw material and consumption and reaction conditions (for example temperature of reaction and reaction pressure).But, the amount of disproportionation reaction catalyzer generally is 0.0001 to 50 weight % based on the weight as the carbonate alkyl aryl ester of raw material.When using disproportionation reaction catalyzer with solid form, preferably, the amount of catalyzer is 0.01 to 75 volume % based on the internal volume of empty reaction vessel.
Carbonate alkyl aryl ester as raw material can contain at least a compound that is selected from alcohol, aromatic hydroxy compound and diaryl carbonate.But, the disproportionation reaction in the step (5) is balanced reaction (being reversible reaction) (referring to following formula (11)), therefore, when the amount of above-claimed cpd in carbonate alkyl aryl ester is big, has the danger of the transformation efficiency reduction of carbonate alkyl aryl ester.
The time of reaction is different because of the type and the internal structure of reaction conditions and reaction vessel in the step (5).But, this reaction times generally is 0.001 to 50 hour, preferred 0.01 to 10 hour, and more preferably 0.05 to 5 hour.Temperature of reaction (being the temperature in the reaction vessel) is different because of the type as the carbonate alkyl aryl ester of raw material.But, this temperature of reaction generally is 50 to 350 ℃, preferred 100 to 280 ℃.Reaction pressure can be decompression, normal atmosphere or superatmospheric pressure, and this depends on as the type of the carbonate alkyl aryl ester of raw material and temperature of reaction.But, this reaction pressure generally is 10Pa to 20MPa.
In step (5), must not use solvent.But, in order to help the operation in the step (5), can use inert solvent.The example of inert solvent comprises ether, aliphatic hydrocrbon, aromatic hydrocarbon, halogenated aliphatic hydrocarbon and halogenated aromatic hydrocarbons.And then step (5) disproportionation reaction can be carried out in that step (5) disproportionation reaction is in the presence of the inert gasses.The example of this class rare gas element comprises nitrogen, helium, argon gas and step (5) disproportionation reaction is the lower boiling organic compound of inert gasification.When utilizing the multistage distillation tower to carry out step (5), can to distillation tower, introduce the lower boiling organic compound of above-mentioned rare gas element or gasification from the bottom of distillation tower when removing the purpose of low-boiling by-products by distillation for promotion.
After step (5) is finished,, reclaim diaryl carbonate thus by ordinary method separation of diaryl carbonates from carbonate alkyl aryl ester, aromatic hydroxy compound, pure and mild catalyzer (if any).
Type about the used reaction vessel of step (5) has no particular limits, and can use the reaction vessel of any conventional.The example of popular response container comprises stirred vessel, multistage stirred vessel and multistage distillation tower.These reaction vessels can separately or be united use.Utilize at least a above-mentioned reaction vessel, can carry out step (5) in mode in batches or continuously.For making molecular balance, preferably utilize the multistage distillation container to generating the consideration that required product direction moves effectively.More preferably, utilize the multistage distillation container to carry out step (5) continuously.
About the used multistage distillation tower of step (5), have no particular limits, as long as it is to have two or more theoretical stages and distillation tower that can continuous still battery.As this multistage distillation tower, can utilize common usefulness any conventional multistage distillation tower in the art.The example of this class multistage distillation tower comprises the tray column that utilizes tower tray, and described tower tray for example is bubble cap disc, screen tray, valve tray or counter-current tray; With the filled-type tower that is filled with various fillers, described filler for example is Raschig ring, Lessing ring, Pall ring, Berl saddle packing, Interlox saddle packing, Dixon filler, MeMahon packing, Heli-Pack packing, sumbul oil and ripple packing.And then, also can preferably utilize the mixed type of tray column and packed tower, it comprises plate part and fills Packed part.
When utilizing the multistage distillation tower to carry out from carbonate alkyl aryl ester production diaryl carbonates continuously in step (5), this production for example is performed as follows.To send into continuously in the multistage distillation tower as the carbonate alkyl aryl ester of raw material, carrying out the disproportionation reaction of carbonate alkyl aryl ester in mutually in liquid phase or in solution-air in the presence of the containing metal catalyzer, produce diaryl carbonate thus, and supervene dialkyl carbonate, wherein take out the high boiling mixture that contains the diaryl carbonate of producing to some extent, take out the low boiling mixture that contains the dialkyl carbonate of supervening by distillation continuously from distillation tower top with gaseous form simultaneously from the distillation tower bottom with liquid form.
Material about the inventive method equipment used has no particular limits; But, this material generally is selected from stainless steel and lass lining material.
Accompanying drawing shows the schema of the inventive method embodiment.But, these embodiment should not be interpreted as limiting the scope of the invention.For example, equipment used of the present invention and device (for example reaction vessel, conduit and still) be not limited to shown in the drawings those, can suitably select based on conventional knowledge and technology in addition.If necessary, can carry out extra step in the methods of the invention.For example, can remove the additional step of the compound of supervening at the production period of required aromatic carbonate.And, can add and remove for example drain steps of above-mentioned degradation compound.In addition, can carry out any various conventional processing step.Equipment used of the present invention can have any conventional device, for example gauger (for example under meter or thermometer), reboiler, pump, condenser or distillation tower.In the methods of the invention, if necessary, can heat, for example utilize steam or heater heats, and if necessary, also can cool off, for example naturally cooling, water cooling or brine refrigeration by ordinary method by ordinary method.In order to improve thermo-efficiency, the operation of the inventive method in each step can make and reach thermal equilibrium in this step.Production unit can design and make and to reclaim final product and intermediate product satisfactorily, with easily with its recirculation.
In the inventive method of producing aromatic carbonate, as shown in Figure 1, can make the alcohol that in step (4), produces be recycled to step (3), and can make the dialkyl carbonate that in step (4), produces be recycled to step (4) as raw material.As shown in Figure 2, can make the alcohol that in step (4), produces be recycled to step (3), and can make the dialkyl carbonate that in step (5), produces be recycled to step (4) as raw material.When the circulation of the circulation of step (1) to (4) or step (1) to (5) repeats at least one time, can obtain aromatic carbonate continuously, wherein there be not the material of waste beyond dewatering basically.
In some cases, can make the pure former state that in step (4), reclaims be recycled to step (3).But, when the alcohol that reclaims in step (4) contains a large amount of aromatic hydroxy compounds and/or a large amount of carboxylated compound, should alcohol by conventional separation method purifying, so that aromatic hydroxy compound and the carboxylated compound total amount in alcohol becomes 1,000ppm or lower, preferred 100ppm or lower.As separation method, preferably adopt fractionation by distillation.The distillation purifying of alcohol preferably utilize distillation tower to carry out step (4), because can carry out simultaneously with the production of aromatic carbonate by reactive distillation.
In some cases, can make the dialkyl carbonate former state that in step (4) and/or step (5), reclaims be recycled to step (4).But, when the dialkyl carbonate that is reclaimed contains impurity, preferably, carry out the purifying of dialkyl carbonate before or concentrate to regulate being recycled to step (4).The example of dialkyl carbonate impurities comprises aromatic hydroxy compound and the by product that generates during above-mentioned transesterification reaction and disproportionation reaction.The example of this class by product comprises dialkyl ether and alkyl aryl ether, and they are that decarboxylation by carbonic ether turns into producing.Purifying or concentrated control method as dialkyl carbonate can adopt ordinary method.In ordinary method, it is preferred utilizing the distillatory method.
As mentioned above, as the ordinary method of producing aromatic carbonate (for example diaryl carbonate), known favourable phosgenation and the oxidisability carbonylation method that utilizes carbon monoxide with phosgene.But, the shortcoming of each these ordinary method is to use chlorine-containing compound as raw material or catalyzer, so that the aromatic carbonate of being produced by ordinary method contains a large amount of chlorine-containing compounds inevitably.The use of this aromatic carbonate in polycarbonate production causes serious problem, the variable color and the degraded of for example passivation of polymerizing catalyst, the polycarbonate produced.And then when using this aromatic carbonate that contains a large amount of chlorine-containing compounds as gasoline or procetane, this aromatic carbonate causes engine or Corrosion of Pipeline.Among former the application WO 03/055840 and WO 04/014840, the inventor disclosed a kind of method of producing carbonic ether, wherein produced carbonic ether and water by carbonic acid gas, pure and mild dialkyl tin alcoholate, and wherein the amount of by product is considerably less.The inventor has successfully improved the above-mentioned technology of application in the past, and has realized the present invention.By the inventive method, can be simply and produce the high purity aromatic carbonate that is substantially devoid of impurity (for example chlorine-containing compound) effectively.
Can be advantageously used for the raw material of polycarbonate, isocyanic ester, polycarbonate diol etc. by the high purity aromatic carbonate of the inventive method production.As the aromatic carbonate that is used to produce each above-mentioned polymkeric substance, diaryl carbonate is preferred.
About in polycarbonate, isocyanic ester and the polycarbonate diol each, give an explaination below.
At first, about polycarbonate, give an explaination below.Diaryl carbonate is known to be the raw material that is used for producing by conventional method of fusion polycarbonate, and this method relates generally to the transesterification reaction of diaryl carbonate and dihydroxyphenyl propane.But, as mentioned above, conventional diaryl carbonate contains a large amount of chlorine-containing compounds.The chlorine-containing compound that diaryl carbonate contains makes the employed catalyst deactivation of the transesterification reaction of diaryl carbonate and dihydroxyphenyl propane.For fear of this shortcoming, can imagine a large amount of use catalyzer.But, the use of a large amount of catalyzer influences the various performances of the polycarbonate of being produced, for example weathering resistance and color nocuously.Therefore, in the conventional method of fusion of this class, must carry out from diaryl carbonate, removing the additional step of chlorine-containing compound.
As the ordinary method of from diaryl carbonate, removing chlorine-containing compound, can mention a kind of like this method, wherein with diaryl carbonate with neutralizing treatment or by distillation purifying.But, this ordinary method has following fatal problem.The washing of diaryl carbonate is to carry out under diaryl carbonate is the temperature of melted state.But, the fusing point of diaryl carbonate is higher, therefore, need carry out under comparatively high temps with the neutralizing treatment diaryl carbonate.Consequently, diaryl carbonate suffers hydrolysis during with neutralizing treatment.On the other hand, when by the distillation purifying diaryl carbonate, be very difficult to from diaryl carbonate, remove chlorine-containing compound satisfactorily, because diaryl carbonate contains the various chlorine-containing compounds that have from low temperature to the pyritous different boiling.Therefore, when planning to obtain having abundant highly purified polycarbonate for commercialization, it is very high that the purifying cost becomes.
Produce in the ordinary method of diaryl carbonate (for example diphenyl carbonate) at another kind, at first by ethylene carbonate (use carbonic acid gas as raw material production) and methanol production methylcarbonate, produce the carbonic acid methyl by methylcarbonate again. phenylester, then by the carbonic acid methyl. phenylester is produced diphenyl carbonate.In this method, must generate methylcarbonate as intermediate product, and with the form distillating carbinol (its boiling point is minimum in reaction system) of the azeotropic mixture of methyl alcohol and methylcarbonate, so that the balance of reaction (being used for by ethylene carbonate and methanol production methylcarbonate) moves to the direction that generates required product.In this method, must supervene the carbonic acid methyl. phenylester.The carbonic acid methyl. phenylester is to the side reaction sensitivity, and is for example responsive to the decarboxylation reaction, generates methylic by product thus, for example phenylmethylether.Methylic by product and required diphenyl carbonate mix, even and attempt the purifying dipheryl carbonate ester and also can not remove this class by product fully from diphenyl carbonate.The existence of methylic by product in diphenyl carbonate causes following point.Polymerization rate by the dpc production polycarbonate reduces.And then, can not obtain having the polycarbonate of even molecular weight.And the polycarbonate of being produced can variable color.
On the other hand, in the methods of the invention, can produce diaryl carbonate and don't produce the disadvantageous by product of this class.In the diaryl carbonate of producing by the inventive method, do not exist methylic by product to be difficult to confirm.But, when producing diaryl carbonate by the inventive method, the intermediate of aromatic carbonate is not limited to methylcarbonate.Therefore, in the methods of the invention, by using the intermediate except that methylcarbonate, can obtain being substantially devoid of the aromatic carbonate of methylic by product, this by product influences the polyreaction of producing polycarbonate unfriendly.
The preferred embodiment that is used as the diaryl carbonate of the raw material of producing polycarbonate comprises such diaryl carbonate, and wherein methylic content of by-products is based on no more than 100 ppm by weight of the weight of diaryl carbonate, more advantageously no more than 10 ppm by weight.
About isocyanic ester, give an explaination below.Use aromatic carbonate of the present invention (especially diaryl carbonate) can produce highly purified isocyanic ester.Particularly, for example, make the reaction of diaryl carbonate and polyamine, obtain carboxylamine polyaryl ester (for example carboxylamine hexa-methylene diaryl ester), make gained carboxylamine polyaryl ester carry out thermolysis, production has highly purified isocyanic ester thus.Usually, as the method with low-cost synthesizing isocyanate, only known use phosgene (chlorine-containing compound) is as the method for raw material.On the other hand, the diaryl carbonate of being produced by the inventive method is cheap, only contains very small amount of chlorine-containing compound (if any).Therefore, it is very favorable that the isocyanic ester that is obtained by diaryl carbonate of the present invention is compared with conventional isocyanic ester, and the latter is by the method production of using phosgene and therefore contain chlorine-containing compound.Isocyanic ester is mainly used in the production urethane.The problem of being produced urethane by conventional isocyanic ester is that the urethane catalyzer is passivation and sex change easily in the presence of chlorine.But, go up substantially from the isocyanic ester of dpc production obtained by the method for the present invention and not contain chlorine-containing compound, therefore do not have the problems referred to above.
About polycarbonate diol, give an explaination below.Use aromatic carbonate of the present invention, can produce highly purified polycarbonate diol.
Polycarbonate of the present invention, isocyanic ester and polycarbonate diol each use the aromatic carbonate produced by the inventive method to produce naturally, and they have the following advantage that is better than conventional polycarbonate, isocyanic ester and polycarbonate diol.Polycarbonate of the present invention, isocyanic ester and polycarbonate diol have high purity, and can be simply produce (therefore cheap) and can not cause generating the problem of by product.Therefore, polycarbonate of the present invention, isocyanic ester and polycarbonate diol have high commercial value.
Preferred forms of the present invention
Below, describing the present invention in detail with reference to the following example and Comparative Examples, these embodiment and Comparative Examples should not be interpreted as limiting the scope of the invention.
In the following example and Comparative Examples, carry out various measurements and analysis by following method.
1) nucleus magnetic resonance of organometallic compound (NMR) is analyzed
Instrument: JNM-A400 FT-NMR system (by JEOL Ltd., Japanese produce and market)
(1) supplies
1H-with
13The preparation of the sample solution that C-NMR analyzes
About 0.1 to the 0.5g organometallic compound of weighing to wherein adding about 0.9g deuterate chloroform, obtains the sample solution of analyzing for NMR then thus.
(2) supply
119The preparation of the sample solution that Sn-NMR analyzes
Weighing about 0.1 to 1g contains the liquid of organic metallic compound, to wherein adding 0.05g tin tetramethide and about 0.85g deuterate chloroform, obtains the sample solution of analyzing for NMR thus then.
2) gas-chromatography of carbonic ether (GC)
Instrument: GC-2010 system (by Shimadzu Corporation, Japanese produce and market)
(1) preparation of sample solution
The liquid of weighing 0.4g its carbonate content to be measured is then to wherein adding about 0.5ml dehydration dimethyl formamide or dehydration acetonitrile.And then, in products therefrom, add about 0.04g toluene or phenyl ether as interior mark, obtain the sample solution that common GC analyzes thus.
(2) GC analysis condition
Pillar: DB-1 is (by J﹠amp; W Scientific, the U.S.A. produce and market)
Liquid phase: 100% dimethyl polysiloxane
Column length: 30m
Column diameter: 0.25mm
Film thickness: 1 μ m
Column temperature: the speed by 10 ℃/min rises to 300 ℃ with temperature from 50 ℃
Injection temperature: 300 ℃
Detector temperature: 300 ℃
Detector: FID (flame ionization detector)
(3) quantitative analysis
Utilization is carried out the quantitative analysis of sample solution about standard model gained calibration curve.
3) calculating of aromatic carbonate productive rate
The productive rate of step (4) gained aromatic carbonate represents with the weight % based on step (4) gained reaction mixture weight, perhaps with based on representing as the gained carbonate alkyl aryl ester of the dialkyl carbonate integral molar quantity of the raw material of step (4) the reaction mole % with diaryl carbonate.
4) number-average molecular weight of aromatic carbonate
Measure the number-average molecular weight of aromatic carbonate by gel permeation chromatography (GPC).
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,224g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is arranged in reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, 5 dischargings of the gaseous emission conduit by being positioned at reaction vessel 1 top simultaneously are the low boiling component of gas form.During reaction, will be transferred to storage tank 7 by condenser 6, in storage tank 7, obtain containing the liquid mixture of 1-fourth alcohol and water from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that reaction vessel 1, obtains from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes in the device 11 of alcohol.
Aforesaid operations is repeated twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, the unreacted alcohol gasification that liquid reaction mixture is contained.From conduit 21, discharge the alcohol of gasification, and be transferred in the storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred in the storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent in the 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), at the bottom of autoclave, take out the gained reaction mixture, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate and be transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,150g (29mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to for the device 11 that removes alcohol by conduit 10, the latter is furnished with agitator, reliever and well heater.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, the gained mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst A that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 4m, the about 5cm of the internal diameter) middle part with 80 screen traies by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and top of tower pressure is 1.2 * 10
5Pa, and reflux ratio is about 3.To be transferred to condenser 41 by conduit 40 from the gas of distillation tower 39 top discharges, make condensation of gas thus.Speed by about 240g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 30g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 9 weight %, about 30 weight % and the dibutyl carbonate of about 61 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the 0.1 weight % that has an appointment, the carbonic acid butyl of about 41 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 50 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 9 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in storage tank 138 is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 240g/h by conduit 59 (being furnished with preheater 60), height 4m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.4m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 189 ℃, and top of tower pressure maintains about 101.3kPa (normal atmosphere), and reflux ratio is about 3.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 16.3g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 223.7g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains have an appointment the 1-butanols of 99.99 weight % and the phenol of about 100 ppm by weight based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains the phenol of the dibutyl carbonate of the 66 weight % that have an appointment, about 33 weight % and the carbonic acid butyl of about 1 weight % based on the weight of this residual liquid. phenylester.
(from water, separating alcohol) by distillation
Device for example shown in Figure 3, by following be alcohol and water by distillation with the condensate separation in the storage tank 7.
The condensation product that to collect in the storage tank 7 in the step (3) of producing dibutyl tin two alcoholate is sent into continuous multi-stage distillation tower 14 (the about 5cm of internal diameter by the speed of about 250g/h continuously by preheater 13, height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position for the above about 0.4m in these distillation tower 14 bottoms, and distill, be alcohol and water with condensate separation thus.During this distillation, the liquid from distillation tower 14 bottoms taking-up distillation tower 14.The liquid that a part is taken out is transferred to reboiler 22 by conduit 15, and then is circulated to distillation tower 14, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 14 bottoms is 81 ℃, and top of tower pressure is reduced to about 20kPa.To be transferred to condenser 18 by conduit 17 from distillation tower 14 top distillatory gases, make condensation of gas thus.The gained condensation product is transferred to gas-liquid separation device 129, is separated into two liquid phases.Take out the bottom phase of condensation product by the speed of about 25g/h continuously from gas-liquid separation device 129 then, and be transferred to storage tank 19.On the other hand, the top of condensation product is back to distillation tower 14 by about 0.6 reflux ratio by conduit 20.Take out residual liquid the distillation tower 14 continuously from distillation tower 14 bottoms by the speed of about 225g/h, and be transferred to storage tank 16 by conduit 15.
The residual liquid of collecting in storage tank 16 contains the almost 1-butanols of 100 weight % based on the weight of this residual liquid, and is substantially devoid of water (detecting less than water in the analysis of residual liquid).On the other hand, the liquid of collecting in storage tank 19 contains the 1-butanols of 75 weight % and the water of 25 weight % based on the weight of liquid in the storage tank 19.
(step (3))
Utilize device shown in Figure 3, after from water, separating alcohol, be performed as follows step (3) by distillation.
The residual liquid that to collect in the storage tank 32 of above-mentioned steps (2) is sent into 5 liters of SUS reaction vessels 1 by conduit 35.And then, the 1-butanols product that to collect in the storage tank 135 of above-mentioned pure recirculation step is sent into reaction vessel 1 by conduit 134,1-butanols product in the storage tank 16 (it is at the fresh 1-butanols of sending into storage tank 16 before the operation of Fig. 3 device and the mixture that is installing isolating unreacted 1-butanols in 11) is sent into reaction vessel 1 by conduit 3, the total amount of wherein sending into the 1-butanols product of reaction vessel 1 is about 2,224g (30mol).In addition, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation at 113 ℃ to the scope of 1-butanols boiling point, react and reach about 6 hours, the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top wherein will be transferred to storage tank 7 by condenser 6 from the gas of conduit 5 dischargings simultaneously.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.From the residual liquid of device 11, collecting, remove unreacted alcohol with above-mentioned same way as then, therefrom remove the residual liquid of alcohol from conduit 12 dischargings, and be collected in the storage tank 23.
The liquid that analysis is collected in storage tank 23.Found that the weight of this liquid is about 107g, this liquid contains have an appointment 0.18mol dibutyl tin two fourth alcoholate and about 0.06 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
After above-mentioned steps (3), be performed as follows step (1).
The liquid of will about 107g collecting in the storage tank 23 of step (3) is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,224g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate and be transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,150g (29mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, the gained mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst A that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is 1 about weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), the about 5cm of internal diameter) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and tower top pressure is 2 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 28 weight %, about 71 weight % and the dibutyl carbonate of about 1 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 11 weight % that have an appointment, about 64 weight %, the carbonic acid butyl of about 22 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 50 bottoms is 237 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 172g/h is taken out the gained condensation product by conduit 55 continuously from condenser 52.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 31g/h, and be transferred to storage tank 58 by conduit 57.
Contain the dibutyl carbonate of the phenol of the 1-butanols of have an appointment 400ppm, about 13 weight %s, about 84 weight %s and the carbonic acid butyl of about 3 weight %s from the condensation product that distillation tower 50 takes out based on the weight of this condensation product by conduit 55. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.1 weight % that has an appointment, the carbonic acid butyl of about 27 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 64 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 9 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 156 ℃, and tower top pressure is about 40kPa, and reflux ratio is about 0.7.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 55g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 146g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 1 weight % that has an appointment and the phenol of about 99 weight % based on the weight of this residual liquid, and is substantially devoid of 1-butanols (detecting less than the 1-butanols in the analysis of residual liquid).
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 310g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.1 weight %, the carbonic acid butyl of about 30 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 70 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 283g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 248 ℃, and tower top pressure is about 27kPa, and reflux ratio is about 4.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 85g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 198g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 0.4 weight %, the carbonic acid butyl of about 99 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 0.2 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.1 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99 weight %, and be substantially devoid of chlorine (in the analysis of residual liquid, detecting) less than chlorine.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,075g (28mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats 11 times (that is to say that aforesaid operations carries out 12 times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 1,280g, this liquid contain have an appointment 2.08mol dibutyl tin two fourth alcoholate and about 0.76 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that will obtain in storage tank 23 is sent into 1 liter of autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by the speed of about 500g/h by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Raise the then internal temperature to 120 ℃ of autoclave is opened above-mentioned valve, introduces the modulated carbon dioxide to 4MPa of pressure in autoclave.React then, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction, the reaction mixture sample of gathering in the autoclave is also analyzed.Found that sample contains the 0.57mol/kg dibutyl carbonate of having an appointment.
Take out reaction mixture the autoclave continuously from autoclave base, and be collected in the storage tank 127.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), the reaction mixture that will collect in storage tank 127 extremely supplies to remove the container 25 of carbonic acid gas by the rate transitions of about 515g/h.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate and be transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will collect in storage tank 32 is sent into 60 liters of SUS reaction vessels 1 by the speed of about 413g/h by conduit 33 and conduit 35.And then by about 7, the speed of 412g/h (100mol/h) is sent into reaction vessel 1 from storage tank 16 by conduit 3, and nitrogen is sent into reaction vessel 1 by the speed of 1.5NL/h by the SUS pipe that is connected with rare gas element conduit 2 with the 1-butanols.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening by speed and the phenol distillation of about 0.25g/h simultaneously.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and tower top pressure is 2 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 27 weight %, about 72 weight % and the dibutyl carbonate of about 1 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 1-butanols of 330 ppm by weight, about 11 weight %, about 65 weight %, the carbonic acid butyl of about 21 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
After step (4), the liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter with 40 screen traies by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), height 2m) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 50 bottoms is 237 ℃, and tower top pressure is about 27kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 172g/h is taken out the gained condensation product continuously from condenser 52, is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 31g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 126 contains the dibutyl carbonate of the phenol of the 1-butanols of the 390ppm that has an appointment, about 13 weight %, about 86 weight % and the carbonic acid butyl of about 1 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of 500 ppm by weight of having an appointment, the carbonic acid butyl of about 26 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 65 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 8 weight %.
Repeat the circulation of above-mentioned steps (1) to (5).
(purifying of diaryl carbonate)
Utilize device shown in Figure 8, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 310g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
After the operation of embodiment 3, repeat the circulation of the following step (1) to (5).
(step (1))
The liquid that will obtain in the storage tank 23 of embodiment 3 steps (3) is sent into 1 liter of autoclave (by Toyo Koatsu Co. by the speed of about 500g/h by conduit 24, Ltd., Japan's produce and market), this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Raise the then internal temperature to 120 ℃ of autoclave is opened above-mentioned valve, introduces the modulated carbon dioxide to 4MPa of pressure in autoclave.React then, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction, the reaction mixture sample of gathering in the autoclave is also analyzed.Found that sample contains the 0.57mol/kg dibutyl carbonate of having an appointment.
Take out reaction mixture the autoclave continuously from autoclave base, and be collected in the storage tank 127.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), the reaction mixture that will collect in storage tank 127 extremely supplies to remove the container 25 of carbonic acid gas by the rate transitions of about 515g/h.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will collect in storage tank 32 is sent into 60 liters of SUS reaction vessels 1 by the speed of about 413g/h by conduit 35.And then by about 7, the speed of 412g/h (100mol/h) is sent into reaction vessel 1 from storage tank 16 by conduit 3, and nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2 with the 1-butanols.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening by speed and the phenol distillation of about 0.25g/h simultaneously.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
The condensation product (containing dibutyl carbonate) that to collect in the storage tank 29 of step (2), the condensation product of collecting in the storage tank 126 of embodiment 3 step 5) (containing dibutyl carbonate), phenol, catalyst B and the liquid of collecting in the storage tank 80 of the purification step of embodiment 3 diaryl carbonates (containing Pb) are mixed together, obtain liquid mixture, its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and tower top pressure is 2 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 27 weight %, about 72 weight % and the dibutyl carbonate of about 1 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 1-butanols of 330 ppm by weight, about 11 weight %, about 65 weight %, the carbonic acid butyl of about 21 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
After step (4), the liquid that will collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter, height 2m) middle part by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), reacts simultaneously thus and distills (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 50 bottoms is 237 ℃, and tower top pressure is about 27kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 172g/h is taken out the gained condensation product by conduit 55 continuously from condenser 52.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 31g/h, and be transferred to storage tank 58 by conduit 57.
Contain the dibutyl carbonate of the phenol of the 1-butanols of have an appointment 390ppm, about 13 weight %s, about 86 weight %s and the carbonic acid butyl of about 1 weight % from the condensation product that condenser 52 takes out based on the weight of this condensation product by conduit 55. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of 500 ppm by weight of having an appointment, the carbonic acid butyl of about 26 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 65 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 8 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of above-mentioned steps (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 67g/h by conduit 59 (being furnished with preheater 60), height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.4m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 164 ℃, and tower top pressure is about 53kPa, and reflux ratio is about 0.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 18.2g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 48.8g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains have an appointment the 1-butanols of 99.9 weight % and the phenol of about 150 ppm by weight based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains the 1-butanols of the dibutyl carbonate of the 1 weight % that has an appointment, about 100 ppm by weight and the phenol of about 98 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in above-mentioned steps (5) storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 315g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 200 ppm by weight, the carbonic acid butyl of about 29 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 71 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 288g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 4m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 198 ℃, and tower top pressure is about 6kPa, and reflux ratio is about 6.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 90g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 198g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 700 ppm by weight, the carbonic acid butyl of about 93 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 7 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the almost diphenyl carbonate of 100 weight % based on the weight of this residual liquid, and is substantially devoid of the carbonic acid butyl. phenylester (the GC analyzing and testing of residual liquid is less than the carbonic acid butyl. phenylester).And then the residual liquid of collecting in storage tank 91 is substantially devoid of chlorine (detecting less than chlorine) in the analysis of residual liquid.
(productions of dioctyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dioctyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 108g (0.3mol) di-n-octyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein di-n-octyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.5NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 12 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 375g, this liquid contains have an appointment 0.50mol dioctyl tin two fourth alcoholate and about 0.20 mol 1,1,3,3-four octyl groups-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 125g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.05mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.06mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 90g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 180 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dioctyl tin two alcoholate by the speed of about 0.04mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 80g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,223g (30mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.5NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 12 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dioctyl tin two fourth alcoholate and 1,1,3,3-four octyl groups-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.Distill excessive phenol then, and take out, obtain catalyst B thus from reaction vessel top.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of internal diameter) middle part by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 239 ℃, and tower top pressure is 250kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 33 weight %, about 65 weight % and the dibutyl carbonate of about 2 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 11 weight % that have an appointment, about 60 weight %, the carbonic acid butyl of about 26 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1.6 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 240 ℃, and tower top pressure is about 27kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 165g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 39g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 126 contains the dibutyl carbonate of the phenol of the 1-butanols of the 500ppm that has an appointment, about 13 weight %, about 85 weight % and the carbonic acid butyl of about 2 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.3 weight % that has an appointment, the carbonic acid butyl of about 32 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 61 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 7 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 59 (being furnished with preheater 60), height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.7m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 145 ℃, and tower top pressure is about 13kPa, and reflux ratio is about 0.3.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 68g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 133g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains have an appointment the 1-butanols of 99.9 weight % and the phenol of about 100 ppm by weight based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 2 weight % that have an appointment and the phenol of about 98 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 195g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 14g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.3 weight %, the carbonic acid butyl of about 34 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 66 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 181g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 232 ℃, and tower top pressure is about 16kPa, and reflux ratio is about 2.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 62g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 119g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 0.6 weight %, the carbonic acid butyl of about 99 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 0.4 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.3 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99.7 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, 75g (0.3mol) dibutyltin oxide and 889g (12mol) 1-butanols pack into (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 300g, this liquid contains have an appointment 0.24mol dibutyl tin two fourth alcoholate and about 0.33 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 100g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.02mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.03mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 80g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 100 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.02mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 77g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will collect in storage tank 32 and about 889g (12mol) 1-butanols are sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of internal diameter) middle part by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 215 ℃, and tower top pressure is 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top expellant gas, make condensation of gas thus.Speed by about 16g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 254g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains have an appointment the 1-butanols of 53 weight % and the phenol of about 47 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 29 weight % that have an appointment, about 60 weight %, the carbonic acid butyl of about 9 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 0.5 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in the storage tank 47 of step (4) is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 254g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 235 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 238g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 16g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product that takes out from distillation tower 50 by conduit 55 contains the dibutyl carbonate of the have an appointment phenol of the 1-butanols of 0.1 weight %, about 31 weight %, about 67 weight % and the carbonic acid butyl of about 1 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.1 weight % that has an appointment, the carbonic acid butyl of about 25 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 58 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 17 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 168g/h by conduit 59 (being furnished with preheater 60), height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.8m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 145 ℃, and tower top pressure is about 27kPa, and reflux ratio is about 0.3.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 90g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 78g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains have an appointment the 1-butanols of 99.9 weight % and the phenol of about 150 ppm by weight based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains the 1-butanols of the dibutyl carbonate of the 0.2 weight % that has an appointment, about 100 ppm by weight and the phenol of about 99 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 163g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.1 weight %, the carbonic acid butyl of about 30 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 70 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 136g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 233 ℃, and tower top pressure is about 17kPa, and reflux ratio is about 3.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 41g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 95g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 0.3 weight %, the carbonic acid butyl of about 99 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 0.3 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.1 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 11, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 103 from container 25, and be collected in the storage tank 137.
The liquid that to collect in storage tank 137 is sent into multistage distillation tower 105 (internal diameter 5cm, height 2m) middle part by the speed of about 106g/h by conduit 136 (being furnished with preheater 104) subsequently, distills thus.During this distillation, the liquid from distillation tower 105 bottoms taking-up distillation tower 105.The liquid that a part is taken out is transferred to reboiler 111 by conduit 112, and then is circulated to distillation tower 105, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 105 bottoms is 170 ℃, and tower top pressure is about 1kPa, and reflux ratio is about 1.To be transferred to condenser 107 by conduit 106 from distillation tower 105 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 110 continuously from condenser 107.Take out the residual liquid the distillation tower 105 from distillation tower 105 bottoms continuously, and be transferred to storage tank 113 by conduit 112.About the gained condensation product that takes out from condenser 107 by conduit 110, discovery has been taken out condensation product by the speed of about 12g/h from condenser 107, and wherein is substantially devoid of dibutyl tin two alcoholate.And then, about the residual liquid that takes out from distillation tower 105, find residual liquid by the rate transitions of about 94g/h to storage tank 113, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 113, collect and about 2,223g (30mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Step (2) gained condensation product (containing dibutyl carbonate), phenol and catalyst B are mixed together, obtain liquid mixture, its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of internal diameter) (having 40 screen traies) middle part by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 230 ℃, and tower top pressure is about 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 22 weight %, about 75 weight % and the dibutyl carbonate of about 3 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 12 weight % that have an appointment, about 68 weight %, the carbonic acid butyl of about 17 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in the storage tank 47 of step (4) is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 237 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 178g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 25g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 126 contains the dibutyl carbonate of the phenol of the 1-butanols of 400 ppm by weight of having an appointment, about 14 weight %, about 83 weight % and the carbonic acid butyl of about 3 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.1 weight % that has an appointment, the carbonic acid butyl of about 34 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 55 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 11 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 59 (being furnished with preheater 60), height 2m) (it is filled with Dixon filler (6mm φ)) middle part, send into the part of position, distill thus for the above about 0.8m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 124 ℃, and tower top pressure is about 9kPa, and reflux ratio is about 0.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 44g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 157g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 4 weight % that have an appointment and the phenol of about 96 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 252g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.1 weight %, the carbonic acid butyl of about 38 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 62 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 225g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 227 ℃, and tower top pressure is about 13kPa, and reflux ratio is about 4.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 87g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 138g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 0.3 weight %, the carbonic acid butyl of about 99 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 0.1 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of 400 ppm by weight of having an appointment based on the weight of this residual liquid. phenylester and the diphenyl carbonate of 100 weight % almost.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,333g (30mol) isopropylcarbinol is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and isopropylcarbinol is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 107 ℃ to the scope of isopropylcarbinol boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, wherein obtain containing the liquid mixture of isobutyl alcohol and water from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.56mol dibutyl tin two isobutyl alcoholate and about 0.17 mol 1,1,3, the 3-tetrabutyl-1,3-two isobutoxy distannoxanes.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain 0.06mol carbonic acid diisobutyl ester in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol carbonic acid diisobutyl ester of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 2.7kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out the carbonic acid diisobutyl ester, and be transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.07mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than the carbonic acid diisobutyl ester.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,150g (29mol) isopropylcarbinol is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and isopropylcarbinol are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 107 ℃ to the scope of isopropylcarbinol boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains the isobutyl alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two isobutyl alcoholate and 1,1,3, the 3-tetrabutyl-1,3-two isobutoxy distannoxanes.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, the gained mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing the carbonic acid diisobutyl ester), phenol and the catalyst A that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its carbonic acid diisobutyl ester/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of internal diameter) (having 40 screen traies) middle part by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and tower top pressure is 2 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 42g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 228g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the phenol of the isopropylcarbinol of the 33 weight % that have an appointment, about 66.5 weight % and the carbonic acid diisobutyl ester of about 0.5 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the carbonic acid diisobutyl ester of the phenol of the 21 weight % that have an appointment, about 62 weight %, the isobutyl carbonate butyl of about 15 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in the storage tank 47 of step (4) is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 228g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 239 ℃, and tower top pressure is about 30kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 206g/h is taken out the gained condensation product by conduit 55 continuously from condenser 52.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 22g/h, and be transferred to storage tank 58 by conduit 57.
Contain the carbonic acid diisobutyl ester of the phenol of the isopropylcarbinol of have an appointment 0.2 weight %, about 23 weight %s, about 73 weight %s and the isobutyl carbonate butyl of about 4 weight %s from the condensation product that condenser 52 takes out based on the weight of this condensation product by conduit 55. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the carbonic acid diisobutyl ester of the 0.1 weight % that has an appointment, the isobutyl carbonate butyl of about 28 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 60 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 12 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 210g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 175 ℃, and tower top pressure is about 80kPa, and reflux ratio is about 0.3.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 69g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 141g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the isopropylcarbinol of the 99.9 weight % that have an appointment and the phenol of about 400 ppm by weight based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains the have an appointment isopropylcarbinol of the carbonic acid diisobutyl ester of 0.7 weight %, about 300 ppm by weight and the phenol of about 99 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 220g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the carbonic acid diisobutyl ester of have an appointment 1,000 ppm by weight, the isobutyl carbonate butyl of about 32 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 68 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 193g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 4m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 211 ℃, and tower top pressure is about 7kPa, and reflux ratio is about 2.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 61g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 132g/h, and be transferred to storage tank 91 by conduit 90.
The condensation product that takes out from condenser 85 by conduit 88 contains the carbonic acid diisobutyl ester of the 0.3 weight % that has an appointment, the carbonic acid butyl of about 99 weight % based on the weight of this condensation product. the diphenyl carbonate of phenylester and about 0.1 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of 500 ppm by weight of having an appointment based on the weight of this residual liquid. phenylester and the diphenyl carbonate of 100 weight % almost.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 4,837g (21mol) 2-ethyl-1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and 2-ethyl-1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 1.0NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
With the heating of the content of reaction vessel 1, stir simultaneously subsequently,, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top so that be about 120 ℃ with its temperature regulation.During reaction, will be transferred to storage tank 7 by condenser 6, wherein obtain containing the liquid mixture of 2-ethyl-1-fourth alcohol and water from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 360g, this liquid contains the 0.60mol dibutyl tin of having an appointment two (2-ethyl-1-fourth alcoholate) and about 0.15mol1, and 1,3, the 3-tetrabutyl-1, two (2-ethyl-1-butoxy) distannoxanes of 3-.
(step (1))
The liquid that about 120g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain two (2-ethyl-butyl) esters of 0.07mol carbonic acid in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain two (2-ethyl-butyl) esters of the 0.08mol carbonic acid of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 90g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 180 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 2.7kPa.Take out volatiles from distillation tower 27, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out two (2-ethyl-butyl) esters of carbonic acid, and be transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 80g/h to storage tank 32, and detect less than carbonic acid pair (2-ethyl-butyl) esters by vapor-phase chromatography (GC).
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 4,837g (21mol) 2-ethyl-1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 2-ethyl-1-butanols is sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 1.0NL/h by the SUS pipe that is connected with rare gas element conduit 2.
With the heating of the content of reaction vessel 1, stir simultaneously subsequently,, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top so that be about 120 ℃ with its temperature regulation.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 2-ethyl-1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two (2-ethyl butanol thing) and 1,1,3, the 3-tetrabutyl-1, two (the 2-ethyl butoxy) distannoxanes of 3-.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, the gained mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
The condensation product that to collect in the storage tank 29 of step (2) (containing two (2-ethyl-butyl) esters of carbonic acid), phenol and catalyst A are mixed together, obtain liquid mixture, its carbonic acid is two, and (2-ethyl-butyl) ester/the phenol weight ratio is 71/29, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of internal diameter) (having 40 screen traies) middle part by the speed of about 200g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 237 ℃, and tower top pressure is 13kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 34g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 166g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the phenol of have an appointment 2-ethyl-1-butanols of 29 weight %, about 70.7 weight % and two (2-ethyl-butyl) esters of carbonic acid of about 0.3 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains two (2-ethyl-butyl) esters of carbonic acid of the phenol of the 14 weight % that have an appointment, about 70 weight %, the carbonic acid 2-ethyl-butyl of about 13 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 0.7 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in the storage tank 47 of step (4) is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 166g/h by conduit 48 (being furnished with preheater 49), height 2m) (having 40 screen traies) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 239 ℃, and tower top pressure is about 19kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 157g/h is taken out the gained condensation product by conduit 55 continuously from condenser 52.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 9g/h, and be transferred to storage tank 58 by conduit 57.
Contain carbonic acid two (2-ethyl-butyl) esters of the phenol of the 2-ethyl-1-butanols of have an appointment 500 ppm by weight, about 15 weight %s, about 78 weight %s and the carbonic acid 2-ethyl-butyl of about 7 weight %s from the condensation product that condenser 52 takes out based on the weight of this condensation product by conduit 55. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains two (2-ethyl-butyl) esters of carbonic acid of the 0.1 weight % that has an appointment, the carbonic acid 2-ethyl-butyl of about 26 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 53 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 21 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 170g/h by conduit 59 (being furnished with preheater 60), height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.4m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 138 ℃, and tower top pressure is about 20kPa, and reflux ratio is about 2.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 49g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 121g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the 2-ethyl-1-butanols of the 99.7 weight % that have an appointment and the phenol of about 0.3 weight % based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains two (2-ethyl-butyl) esters of carbonic acid of the 0.4 weight % that has an appointment, 2-ethyl-1-butanols of about 0.1 weight % and the phenol of about 99.5 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 193g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 230 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.5.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 40g/h, and be transferred to storage tank 80 by conduit 79.
Contain carbonic acid two (2-ethyl-butyl) esters of have an appointment 0.1 weight %, the carbonic acid 2-ethyl-butyl of about 33 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 67 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 229g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 4m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.2m in these distillation tower 83 bottoms.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 241 ℃, and tower top pressure is about 33kPa, and reflux ratio is about 5.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 120g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 109g/h, and be transferred to storage tank 91 by conduit 90.
Contain carbonic acid two (2-ethyl-butyl) esters of have an appointment 0.2 weight %, the carbonic acid 2-ethyl-butyl of about 61 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 39 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid 2-ethyl-butyl of the 2 weight % that have an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 98 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 100 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.05mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.06mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 90g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 120 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.05mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 80g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,223g (30mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), the about 5cm of internal diameter) (has 40 screen traies), send into the part of position, react simultaneously thus and distill (being reactive distillation) for the above about 0.5m in these distillation tower 39 bottoms.During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 221 ℃, and tower top pressure is 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 42g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 23 weight %, about 73 weight % and the dibutyl carbonate of about 4 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 12 weight % that have an appointment, about 67 weight %, the carbonic acid butyl of about 18 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 235 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 176g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 29 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 27g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 29 contains the dibutyl carbonate of the phenol of the 1-butanols of 300 ppm by weight of having an appointment, about 14 weight %, about 84 weight % and the carbonic acid butyl of about 1 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.5 weight % that has an appointment, the carbonic acid butyl of about 31 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 59 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 10 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 116 ℃, and tower top pressure is about 13kPa, and reflux ratio is about 0.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 46g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 155g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product that takes out from condenser 63 by conduit 66 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 5 weight % that have an appointment and the phenol of about 95 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 273g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.6 weight %, the carbonic acid butyl of about 34 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 65 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 246g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 211 ℃, and tower top pressure is about 7kPa, and reflux ratio is about 2.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 85g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 161g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 1.6 weight %s, the carbonic acid butyl of about 98 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 0.4 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.2 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol all is transferred to storage tank 23 by conduit 12 then.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 1,170g, this liquid contain have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 130g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.01mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.02mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.Take out the gained mixture from autoclave base then, be transferred to the storage tank 127 of device as shown in Figure 4.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).After the operation, analyze gained reaction mixture sample in the storage tank 127 for the third time.Found that the gained reaction mixture contains the 0.07mol dibutyl carbonate.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
The reaction mixture that to collect in the storage tank 127 of step (1) is transferred to for the container 25 that removes carbonic acid gas by conduit 128.Then the reaction mixture in the container 25 was heated about 15 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, remove the carbonic acid gas that therefrom discharges from container.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 26g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 120 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate and 1-butanols, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.02mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 22g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,223g (30mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(from dialkyl carbonate, separating alcohol)
Utilize device shown in Figure 10, by following be pure and mild dialkyl carbonate with the condensate separation in the storage tank 29 of step (2).
The condensation product that to collect in the storage tank 29 of step (2) is sent into continuous multi-stage distillation tower 94 (the about 5cm of internal diameter by the speed of about 295g/h by conduit 92 (being furnished with preheater 93), height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position for the above about 0.6m in these distillation tower 94 bottoms, distill, be pure and mild dialkyl carbonate with condensate separation thus, just be separated into 1-butanols and dibutyl carbonate.During this distillation, the liquid from distillation tower 94 bottoms taking-up distillation tower 94.The liquid that a part is taken out is transferred to reboiler 100 by conduit 101, and then is circulated to distillation tower 94, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 94 bottoms is 150 ℃, and its tower top pressure is reduced to about 19kPa, and reflux ratio is about 0.1.To be transferred to condenser 96 by conduit 95 from distillation tower 94 top distillatory gases, make condensation of gas thus.The gained condensation product is transferred to storage tank 139 by the speed of about 283g/h by conduit 99.Take out residual liquid the distillation tower 94 continuously from distillation tower 94 bottoms by the speed of about 12g/h, and be transferred to storage tank 102 by conduit 101.
The residual liquid of collecting in storage tank 139 contains the almost 1-butanols of 100 weight % based on the weight of this residual liquid, and is substantially devoid of dibutyl carbonate (by the GC analyzing and testing of residual liquid less than dibutyl carbonate).On the other hand, the liquid of collecting in storage tank 102 contains the dibutyl carbonate of the 99.6 weight % that have an appointment and the 1-butanols of about 0.4 weight % based on the weight of liquid in the storage tank 102.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of internal diameter) (having 40 screen traies) middle part by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 220 ℃, and tower top pressure is 150kPa, and reflux ratio is about 1.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 203g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 18 weight %, about 74 weight % and the dibutyl carbonate of about 8 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 14 weight % that have an appointment, about 69 weight %, the carbonic acid butyl of about 14 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 203g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 231 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 1.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 181g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 29 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 22g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 29 contains the dibutyl carbonate of the phenol of the 1-butanols of 500 ppm by weight of having an appointment, about 16 weight %, about 82 weight % and the carbonic acid butyl of about 2 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.1 weight % that has an appointment, the carbonic acid butyl of about 38 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 50 weight %.And then the residual liquid of collecting in storage tank 58 has the Pb content of about 12 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 134 ℃, and tower top pressure is about 16kPa, and reflux ratio is about 0.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 38g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 163g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 10 weight % that have an appointment and the phenol of about 90 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The residual liquid that to collect in the storage tank 58 of step (5) is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter by the speed of about 225g/h by conduit 70 (being furnished with preheater 71), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.1 weight %, the carbonic acid butyl of about 43 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 57 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 198g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 211 ℃, and tower top pressure is about 7kPa, and reflux ratio is about 2.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 86g/h is taken out the gained condensation product by conduit 88 continuously from condenser 85.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 112g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 0.3 weight %, the carbonic acid butyl of about 99 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 0.2 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.1 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from conduit 5 distillatory gases.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 120g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), distills under about 0.5 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.08mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 110g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,223g (30mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from conduit 5 distillatory gases, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is about 48/52, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 221 ℃, and tower top pressure is about 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 60g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 210g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 10 weight %, about 90 weight % and the dibutyl carbonate of about 0.3 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 36 weight % that have an appointment, about 54 weight %, the carbonic acid butyl of about 8 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 0.5 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 210g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 237 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make condensation of gas thus.Speed by about 198g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 12g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 126 contains the dibutyl carbonate of the have an appointment phenol of the 1-butanols of 0.4 weight %, about 38 weight %, about 60 weight % and the carbonic acid butyl of about 1 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 1 weight % that has an appointment, the carbonic acid butyl of about 11 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 65 weight %.And then the liquid of collecting in storage tank 58 has the Pb content of about 23 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in storage tank 138 is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 300g/h by conduit 59 (being furnished with preheater 60), distills thus.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 134 ℃, and tower top pressure is about 16kPa, and reflux ratio is about 0.7.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make condensation of gas thus.Speed by about 30g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 270g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 0.3 weight % that has an appointment and the phenol of about 99 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The condensation product that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 118g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make condensation of gas thus.Take out the gained condensation product by conduit 77 continuously from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 1 weight %, the carbonic acid butyl of about 15 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 84 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 91g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 207 ℃, and tower top pressure is about 5kPa, and reflux ratio is about 3.5.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 14g/h is taken out the gained condensation product continuously from condenser 85, and shifts by conduit 88.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 77g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 8 weight %s, the carbonic acid butyl of about 90 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 2 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.2 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,224g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 150 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.07mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,150g (29mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the ethanol hafnium that to collect in the storage tank 22 of step (2) are (by Gelest Inc., U.S.A. produce and market) be mixed together, obtain liquid mixture, its dibutyl carbonate/phenol weight ratio is 65/35, and Hf content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and tower top pressure is 2 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 40g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 230g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 27 weight %, about 70 weight % and the dibutyl carbonate of about 1 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 21 weight % that have an appointment, about 62 weight %, the carbonic acid butyl of about 11 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter with 40 screen traies by the speed of about 230g/h by conduit 48 (being furnished with preheater 49), height 2m) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 239 ℃, and tower top pressure is about 20kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 220g/h is taken out the gained condensation product continuously from condenser 52, and shifts by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 15g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product that takes out from condenser 52 by conduit 55 contains the dibutyl carbonate of the have an appointment phenol of the 1-butanols of 1 weight %, about 22 weight %, about 68 weight % and the carbonic acid butyl of about 2 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the diphenyl carbonate of the dibutyl carbonate of the 0.1 weight % that has an appointment, about 50 weight % and the carbonic acid butyl of about 31 weight % based on the weight of this residual liquid. phenylester.And then the liquid of collecting in storage tank 58 has the Pb content of about 18 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 200g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 121 ℃, and tower top pressure is about 9kPa, and reflux ratio is about 0.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 54g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 146g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 1 weight % that has an appointment and the phenol of about 96 weight % based on the weight of this residual liquid, and is substantially devoid of 1-butanols (detecting less than the 1-butanols in the analysis of residual liquid).
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The condensation product that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 149g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product continuously and pass through conduit 77 transfers from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 0.1 weight %, the carbonic acid butyl of about 50 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 50 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 122g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 227 ℃, and tower top pressure is about 13kPa, and reflux ratio is about 4.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Taking out the gained condensation product by the speed of about 61g/h continuously from condenser 85 also shifts by conduit 88.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 61g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 0.2 weight %, the carbonic acid butyl of about 99 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 300 ppm by weight.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of 400 ppm by weight of having an appointment based on the weight of this residual liquid. phenylester and the diphenyl carbonate of 100 weight % almost.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 60g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.1 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 140 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 2kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.04mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 55g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,223g (30mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the diphenyl tin oxide that to collect in the storage tank 29 of step (2) are (by Azmax Co.Ltd., Japan's produce and market) is mixed together, obtain liquid mixture, its dibutyl carbonate/phenol weight ratio is about 65/35, and Sn content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 135g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 231 ℃, and tower top pressure is about 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 31g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 105g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 8 weight %, about 84 weight % and the dibutyl carbonate of about 8 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 17 weight % that have an appointment, about 75 weight %, the carbonic acid butyl of about 6 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 0.3 weight %.And then the liquid of collecting in storage tank 47 has the Sn content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 316g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 240 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 304g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 12g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 29 contains the dibutyl carbonate of the have an appointment phenol of the 1-butanols of 0.1 weight %, about 18 weight %, about 79 weight % and the carbonic acid butyl of about 3 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.5 weight % that has an appointment, the carbonic acid butyl of about 40 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 25 weight %.And then the liquid of collecting in storage tank 58 has the Sn content of about 34 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 310g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 110 ℃, and tower top pressure is about 9kPa, and reflux ratio is about 0.7.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 25g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 285g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 9 weight % that have an appointment and the phenol of about 91 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The condensation product that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 200g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product continuously and pass through conduit 77 transfers from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 70g/h, and be transferred to storage tank 80 by conduit 79.
The condensation product that shifts by conduit 77 contains the dibutyl carbonate of the 1 weight % that has an appointment, the carbonic acid butyl of about 61 weight % based on the weight of this condensation product. the diphenyl carbonate of phenylester and about 38 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 130g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 227 ℃, and tower top pressure is about 13kPa, and reflux ratio is about 4.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 81g/h is taken out the gained condensation product continuously from condenser 85, and shifts by conduit 88.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 49g/h, and be transferred to storage tank 91 by conduit 90.
The condensation product that shifts by conduit 88 contains the dibutyl carbonate of the 2 weight % that have an appointment, the carbonic acid butyl of about 98 weight % based on the weight of this condensation product. the diphenyl carbonate of phenylester and about 0.1 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the almost diphenyl carbonate of 100 weight % based on the weight of this residual liquid, and is substantially devoid of the carbonic acid butyl. phenylester (in the analysis of residual liquid, detect less than the carbonic acid butyl. phenylester).
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 3,486g (30mol) 5-methyl isophthalic acid-hexanol is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and 5-methyl isophthalic acid-hexanol is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
With the heating of the content of reaction vessel 1, stir simultaneously subsequently,, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top so that be about 120 ℃ with its temperature regulation.During reaction, will be transferred to storage tank 7 by condenser 6, wherein obtain containing the liquid mixture of 5-methyl isophthalic acid-own alcohol and water from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 380g, this liquid contains the 0.56mol dibutyl tin of having an appointment two (ownization of 5-methyl thing) and about 0.17 mol 1,1,3, the 3-tetrabutyl-1,3-two (5-methyl hexyl) distannoxane.
(step (1))
The liquid that about 127g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain 0.07mol carbonic acid two (2-ethyl-butyl) ester in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.08mol carbonic acid two of having an appointment (5-methyl hexyl) ester in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 60g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.5 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 100 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out carbonic acid two (5-methyl hexyl) ester, and be transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.04mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 55g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than carbonic acid two (5-methyl hexyl) ester.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 3,486g (30mol) 5-methyl isophthalic acid-hexanol is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 5-methyl isophthalic acid-hexanol are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
With the heating of the content of reaction vessel 1, stir simultaneously subsequently,, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top so that be about 120 ℃ with its temperature regulation.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 5-methyl isophthalic acid-own alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two (ownization of 5-methyl thing) and 1,1,3, the 3-tetrabutyl-1,3-two (5-methyl hexyl) distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
The condensation product that to collect in the storage tank 29 of step (2) (containing carbonic acid two (5-methyl hexyl) ester), phenol and catalyst B are mixed together, obtain liquid mixture, its carbonic acid two (5-methyl hexyl) ester/phenol weight ratio is about 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), the about 5cm of internal diameter) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 230 ℃, and tower top pressure is about 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 58g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 212g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of 5-methyl isophthalic acid-hexanol of 21 weight %, about 79 weight % and the carbonic acid two of about 0.3 weight % (5-methyl hexyl) ester based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the carbonic acid 5-methyl hexyl of the phenol of the 29 weight % that have an appointment, the carbonic acid two of about 60 weight % (5-methyl hexyl) ester, about 9 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 0.5 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in the storage tank 47 of step (4) is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 212g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 237 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 200g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 12g/h, and be transferred to storage tank 58 by conduit 57.
The carbonic acid 5-methyl hexyl that contains the phenol of 5-methyl isophthalic acid-hexanol of 0.1 weight %, about 7 weight % of having an appointment, the carbonic acid two of about 89 weight % (5-methyl hexyl) ester and about 4 weight % by conduit 55 from the condensation product of distillation tower 50 taking-ups based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains carbonic acid two (the 5-methyl hexyl) ester of the 3 weight % that have an appointment, the carbonic acid 5-methyl hexyl of about 15 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 60 weight %.And then the liquid of collecting in storage tank 58 has the Pb content of about 2 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 174g/h by conduit 59 (being furnished with preheater 60), height 2m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, distill thus for the above about 0.4m in these distillation tower 61 bottoms.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 112 ℃, and tower top pressure is about 4kPa, and reflux ratio is about 6.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 36g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 138g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains almost 5-methyl isophthalic acid-hexanol of 100 weight % and the phenol of about 400 ppm by weight based on the weight of this condensation product.On the other hand, the residual liquid of collecting in storage tank 69 contains carbonic acid two (the 5-methyl hexyl) ester of the 0.4 weight % that has an appointment, 5-methyl isophthalic acid-hexanol of about 0.5 weight % and the phenol of about 99 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The condensation product that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 244g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product continuously and pass through conduit 77 transfers from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 54g/h, and be transferred to storage tank 80 by conduit 79.
Contain carbonic acid two (the 5-methyl hexyl) ester of have an appointment 4 weight %s, the carbonic acid 5-methyl hexyl of about 19 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester and about 70 weight %.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 190g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 300 ℃, and tower top pressure is about 101.3kPa (normal atmosphere), and reflux ratio is about 6.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Taking out the gained condensation product by the speed of about 87g/h continuously from condenser 85 also shifts by conduit 88.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 103g/h, and be transferred to storage tank 91 by conduit 90.
Contain carbonic acid two (the 5-methyl hexyl) ester of have an appointment 8 weight %s, the carbonic acid 5-methyl hexyl of about 37 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester and about 55 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid 5-methyl hexyl of the 4 weight % that have an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 96 weight %.
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,224g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 100g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is 130 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
(step (3))
Utilize device shown in Figure 3, be performed as follows step (3).
After step (2), the residual liquid that will in storage tank 32, collect and about 2,150g (29mol) 1-butanols is sent into 5 liters of SUS reaction vessels 1, and wherein residual liquid and 1-butanols are sent into by conduit 35 and conduit 3 respectively.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with rare gas element conduit 2.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will shift by condenser 6 from the gas of conduit 5 dischargings, the gained condensation product, the liquid mixture that just contains 1-fourth alcohol and water is transferred to storage tank 7.After the reaction, the residual liquid from get material conduit 8 taking-up reaction vessels 1, and be transferred to storage tank 9.From storage tank 9, residual liquid is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.The residual liquid that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the residual liquid thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Residual liquid in the discharge equipment 11 (therefrom having removed alcohol), and be transferred to storage tank 23 by conduit 12.
The liquid that analysis is collected in storage tank 23.Found that this liquid contains dibutyl tin two fourth alcoholate and 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
Make the liquid of in storage tank 23, collecting be recycled to step (1), and repeat the circulation of step (1) to (3).
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst A that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 10 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m by the speed of about 180g/h continuously by conduit 37 (being furnished with preheater 38), the about 5cm of internal diameter) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 240 ℃, and tower top pressure is 1.5 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 35g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 145g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 29 weight %, about 71 weight % and the dibutyl carbonate of about 0.2 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 13 weight % that have an appointment, about 56 weight %, the carbonic acid butyl of about 17 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester, about 1 weight % and the butyl of 0.7 weight %. and phenyl ether.And then the liquid of collecting in storage tank 47 has the Pb content of about 12 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 219g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature at the liquid of distillation tower 50 bottoms is 235 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 164g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 52g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 126 contains the dibutyl carbonate of the have an appointment phenol of the 1-butanols of 0.1 weight %, about 17 weight %, about 80 weight %, the carbonic acid butyl of about 1 weight % based on the weight of this condensation product. the butyl of phenylester and about 1.5 weight %. and phenyl ether.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.5 weight % that has an appointment, the carbonic acid butyl of about 17 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester, about 30 weight % and the butyl of about 0.2 weight %. and phenyl ether.And then the liquid of collecting in storage tank 58 has the Pb content of about 52 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 210g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 130 ℃, and tower top pressure is about 9kPa, and reflux ratio is about 0.7.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 61g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 149g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 0.3 weight % that has an appointment and the phenol of about 99 weight % based on the weight of this residual liquid, and is substantially devoid of 1-butanols (detecting less than the 1-butanols in the analysis of residual liquid).
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The condensation product that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 346g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product continuously and pass through conduit 77 transfers from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 180g/h, and be transferred to storage tank 80 by conduit 79.
Contain the dibutyl carbonate of have an appointment 1 weight %, the carbonic acid butyl of about 36 weight %s from the condensation product that condenser 74 takes out based on the weight of this condensation product by conduit 77. the diphenyl carbonate of phenylester, about 62 weight % and the butyl of 0.4 weight %. phenyl ether.
To send into continuous multi-stage distillation tower 83 (internal diameter about 5cm by the speed of about 167g/h by conduit 81 (being furnished with preheater 82) from the condensation product that condenser 74 takes out by conduit 77 subsequently, height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 218 ℃, and tower top pressure is about 9kPa, and reflux ratio is about 5.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 63g/h is taken out the gained condensation product continuously from condenser 85, and is transferred to storage tank 140 by conduit 88.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 104g/h, and be transferred to storage tank 91 by conduit 90.
Contain the dibutyl carbonate of have an appointment 3 weight %s, the carbonic acid butyl of about 96 weight %s from the condensation product that condenser 85 takes out based on the weight of this condensation product by conduit 88. the diphenyl carbonate of phenylester, about 400 ppm by weight and the butyl of about 1 weight %. phenyl ether.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of 300 ppm by weight of having an appointment based on the weight of this residual liquid. phenylester and the diphenyl carbonate of 100 weight % almost.
(recirculation of dialkyl carbonate)
Utilize device shown in Figure 12, be performed as follows the recirculation of dialkyl carbonate.
Condensation product is sent into continuous multi-stage distillation tower 116 (the about 5cm of internal diameter by the speed of about 189g/h by conduit 114 (being furnished with preheater 115) will (to be taken out to storage tank 140 from distillation tower 83 tops by conduit 88 in above-mentioned diaryl carbonate purification step), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 116 bottoms taking-up distillation tower 116.The liquid that a part is taken out is transferred to reboiler 122 by conduit 123, and then is circulated to distillation tower 116, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 116 bottoms is 165 ℃, and tower top pressure is about 9kPa, and reflux ratio is about 6.To be transferred to condenser 118 by conduit 117 from distillation tower 116 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 4.5g/h is taken out the gained condensation product continuously from condenser 118, and is transferred to storage tank 125 by conduit 121.Press the residual liquid of speed from the continuous taking-up in its bottom distillation tower 116 of about 184.5g/h, and be transferred to storage tank 124 by conduit 123.
The condensation product that is taken out to storage tank 125 by conduit 121 contains the dibutyl carbonate of the 96 weight % that have an appointment, the butyl of about 2.5 weight % based on the weight of this condensation product. the carbonic acid butyl of phenyl ether and about 1.5 weight %. and phenylester.On the other hand, the residual liquid of collecting in storage tank 124 contains the dibutyl carbonate of the 0.5 weight % that has an appointment, the butyl of about 1 weight % based on the weight of this residual liquid. the carbonic acid butyl of phenyl ether, about 98 weight %. and the diphenyl carbonate of phenylester and about 400 ppm by weight.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst A that to collect in above-mentioned dialkyl carbonate recirculation step in the storage tank 125 are mixed together, obtain liquid mixture, its dibutyl carbonate/phenol weight ratio is 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), the about 5cm of internal diameter) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 240 ℃, and tower top pressure is 1.5 * 10
5Pa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 51g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 219g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 29 weight %, about 71 weight % and the dibutyl carbonate of about 0.2 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 13 weight % that have an appointment, about 55 weight %, the carbonic acid butyl of about 17 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester, about 1 weight % and the butyl of 3.5 weight %. and phenyl ether.And then the liquid of collecting in storage tank 47 has the Pb content of about 11 weight %.
Comparative Examples 1
By following production aromatic carbonate, wherein do not carry out step (2) or (3).
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.Reaction mixture after reaction is taken out in the autoclave bottom, and be transferred to storage tank.
Repeat above-mentioned dibutyl tin two alcoholate production stages and step (1).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank of step (1) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is about 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 300g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 230 ℃, and tower top pressure is about 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 76g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 224g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains have an appointment the 1-butanols of 98 weight % and the dibutyl carbonate of about 2 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the 13 weight % that have an appointment and the carbonic acid butyl of about 3 weight % based on the weight of this liquid of collecting in storage tank 47. phenylester.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(recirculation of pure and mild aromatic carbonate)
Utilize device shown in Figure 10, the following recirculation of carrying out pure and mild aromatic carbonate.
Condensation product is sent into continuous multi-stage distillation tower 94 (the about 5cm of internal diameter by the speed of about 220g/h by conduit 92 (being furnished with preheater 93) will (to be taken out to storage tank 138 by conduit 44 from condenser 41 in step (4)), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 94 bottoms taking-up distillation tower 94.The liquid that a part is taken out is transferred to reboiler 100 by conduit 101, and then is circulated to distillation tower 94, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 94 bottoms is 207 ℃, and tower top pressure is about 101.3kPa (normal atmosphere), and reflux ratio is about 0.5.To be transferred to condenser 96 by conduit 95 from distillation tower 94 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 216g/h is taken out the gained condensation product continuously from condenser 96, and is transferred to pure storage tank 139 by conduit 99.Take out residual liquid the distillation tower 94 continuously from distillation tower 94 bottoms by the speed of about 216g/h, and be transferred to pure storage tank 135 by conduit 99.
The condensation product of collecting in pure storage tank 139 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol, also is substantially devoid of dibutyl carbonate (detecting less than phenol and dibutyl carbonate in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 102 contains the almost dibutyl carbonate of 100 weight % based on the weight of this residual liquid, and be substantially devoid of butanols, also be substantially devoid of phenol (in the analysis of residual liquid, detecting) less than butanols and phenol.
Comparative Examples 2
By following production aromatic carbonate, wherein do not carry out step (3).
(productions of dibutyl tin two alcoholate)
Utilize device shown in Figure 3, by following production dibutyl tin two alcoholate.
In 5 liters of SUS reaction vessels 1 being furnished with agitator, well heater and baffle plate, pack into 75g (0.3mol) dibutyltin oxide and 2,223g (30mol) 1-butanols is (by Aldrich, U.S.A. produce and market), wherein dibutyltin oxide is to send into by the conduit 4 that is positioned at reaction vessel 1 top, and the 1-butanols is to send into by the conduit 3 that is positioned at reaction vessel 1 top from pure storage tank 16.And then, nitrogen is sent into reaction vessel 1 by the speed of 0.1NL/h by the SUS pipe that is connected with the rare gas element conduit 2 that is positioned at reaction vessel 1 bottom.
Content with reaction vessel 1 heats subsequently, stir simultaneously, so that with its temperature regulation 113 ℃ to the scope of 1-butanols boiling point, react thus and reach about 6 hours, simultaneously the low boiling component of the gaseous emission conduit 5 emission gases forms by being positioned at reaction vessel 1 top.During reaction, will be transferred to storage tank 7 by condenser 6, obtain containing the liquid mixture of 1-fourth alcohol and water therein from the gas of conduit 5 dischargings.After the reaction, take out the liquid reaction mixture that obtains the reaction vessel 1 from getting material conduit 8, and be transferred to storage tank 9.From storage tank 9, liquid reaction mixture is transferred to by conduit 10 be furnished with agitator, the confession of reliever and well heater removes the device 11 of alcohol.
Aforesaid operations repeats twice (that is to say that aforesaid operations carries out three times altogether).The liquid reaction mixture that to collect in for the device 11 that removes alcohol under reduced pressure heats then, makes the unreacted alcohol gasification that contains in the liquid reaction mixture thus.The alcohol of gasification discharges from conduit 21, and is transferred to storage tank 16 by condenser 6.Discharging therefrom removes pure residual liquid 11 from installing, and is transferred to storage tank 23 by conduit 12.
The liquid that analysis obtains in storage tank 23.Found that the weight of this liquid is about 320g, this liquid contains have an appointment 0.54mol dibutyl tin two fourth alcoholate and about 0.18 mol 1,1,3, the 3-tetrabutyl-1,3-dibutoxy distannoxane.
(step (1))
The liquid that about 107g obtains in storage tank 23 is sent into 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) by conduit 24, and this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.06mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.07mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
Utilize device shown in Figure 4, be performed as follows step (2).
After step (1), take out the gained reaction mixture from autoclave base, and be transferred to for the container 25 that removes carbonic acid gas by conduit 133, wherein the atmosphere in the container 25 has been used the nitrogen purging mistake.Then the reaction mixture in the container 25 was heated about 5 minutes in nitrogen atmosphere under 80 ℃, stir simultaneously, from container 25, remove the carbonic acid gas that therefrom discharges.Take out the gained mixture by conduit 26 from container 25, and be collected in the storage tank 131.
Connect the multistage distillation tower 27 (internal diameter 5cm) that is filled with Dixon filler (6mm φ) to thin film distillation device 30 (E-420 is by Sibata Scientific Technology Ltd., Japanese produce and market).The liquid that to collect in storage tank 131 is sent into multistage distillation tower 27 by the speed of about 90g/h by conduit 132 (it is positioned at the middle part of distillation tower 27), and distills under about 0.2 reflux ratio.Thin film distillation device 30 is furnished with heating jacket, and wherein temperature is arranged is about 145 ℃ heating medium in circulation, reduces internal pressure (tower top pressure) to about 1.3kPa.Take out volatiles from distillation tower 27 tops, and be transferred to condenser 28, make the volatiles condensation, the gained condensation product is collected in the storage tank 29.Take out residual liquid in the thin film distillation device 30 by pump, and be transferred to storage tank 32 by conduit 31.About the volatiles that takes out from distillation tower 27 tops, find to have taken out dibutyl carbonate, and it is transferred to storage tank 29, and wherein be substantially devoid of dibutyl tin two alcoholate by the speed of about 0.06mol/h.And then, about the residual liquid that takes out from thin film distillation device 30, find residual liquid by the rate transitions of about 90g/h to storage tank 32, and by vapor-phase chromatography (GC) detection less than dibutyl carbonate.
Repeat above-mentioned dibutyl tin two alcoholate steps, step (1) and step (2).
(step (4))
(Preparation of catalysts)
79g phenol and 32g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, wherein the amount of dephlegmate is about 2.5g.From the excessive phenol of reaction vessel top distillation, obtain catalyst B thus then.
(production of aromatic carbonate)
Utilize device shown in Figure 5, be performed as follows step (4).
Condensation product (containing dibutyl carbonate), phenol and the catalyst B that to collect in the storage tank 29 of step (2) are mixed together, and obtain liquid mixture, and its dibutyl carbonate/phenol weight ratio is about 65/35, and Pb content is about 1 weight %.The gained liquid mixture is sent into continuous multi-stage distillation tower 39 (height 2m, the about 5cm of the internal diameter) middle part with 40 screen traies by the speed of about 270g/h continuously by conduit 37 (being furnished with preheater 38), react simultaneously thus and distill (being reactive distillation).During this reactive distillation, the liquid from distillation tower 39 bottoms taking-up distillation tower 39.The liquid that a part is taken out is transferred to reboiler 45 by conduit 46, and then is circulated to distillation tower 39, so that for reacting and distill the sufficient heat of supply.This reactive distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 39 bottoms is 221 ℃, and tower top pressure is about 150kPa, and reflux ratio is about 2.To be transferred to condenser 41 by conduit 40 from distillation tower 39 top distillatory gases, make condensation of gas thus.Speed by about 67g/h is taken out the gained condensation product from condenser 41, and is transferred to storage tank 138 by conduit 44.Press the liquid of speed from distillation tower 39 bottoms taking-up distillation tower 39 of about 201g/h, and be transferred to storage tank 47 by conduit 46.
The condensation product of collecting in storage tank 138 contains the have an appointment phenol of the 1-butanols of 23 weight %, about 73 weight % and the dibutyl carbonate of about 4 weight % based on the weight of this condensation product.On the other hand, the liquid of collecting in storage tank 47 contains the dibutyl carbonate of the phenol of the 12 weight % that have an appointment, about 67 weight %, the carbonic acid butyl of about 18 weight % based on the weight of this liquid of collecting in storage tank 47. the diphenyl carbonate of phenylester and about 1 weight %.And then the liquid of collecting in storage tank 47 has the Pb content of about 1 weight %.
(step (5))
Utilize device shown in Figure 6, be performed as follows step (5).
The liquid that to collect in storage tank 47 is sent into continuous multi-stage distillation tower 50 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 48 (being furnished with preheater 49), height 2m) (it is filled with Dixon filler (6mm φ)) middle part is reacted simultaneously thus and is distilled (being reactive distillation).During this reactive distillation, the liquid from distillation tower 50 bottoms taking-up distillation tower 50.The liquid that a part is taken out is transferred to reboiler 56 by conduit 57, and then is circulated to distillation tower 50, so that for reacting and distill the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of collecting in distillation tower 50 bottoms is 235 ℃, and tower top pressure is about 26kPa, and reflux ratio is about 2.To be transferred to condenser 52 by conduit 51 from distillation tower 50 top distillatory gases, make the distillatory condensation of gas thus.Speed by about 176g/h is taken out the gained condensation product continuously from condenser 52, and is transferred to storage tank 126 by conduit 55.Take out residual liquid the distillation tower 50 continuously from distillation tower 50 bottoms by the speed of about 27g/h, and be transferred to storage tank 58 by conduit 57.
The condensation product of collecting in storage tank 126 contains the dibutyl carbonate of the phenol of the 1-butanols of 300 ppm by weight of having an appointment, about 14 weight %, about 84 weight % and the carbonic acid butyl of about 1 weight % based on the weight of this condensation product. phenylester.On the other hand, the residual liquid of collecting in storage tank 58 contains the dibutyl carbonate of the 0.5 weight % that has an appointment, the carbonic acid butyl of about 31 weight % based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 59 weight %.And then the liquid of collecting in storage tank 58 has the Pb content of about 10 weight %.
(recirculation of alcohol)
Utilize device shown in Figure 7, be performed as follows the recirculation of alcohol.
The condensation product that to collect in the storage tank 138 of step (4) is sent into continuous multi-stage distillation tower 61 (the about 5cm of internal diameter by the speed of about 201g/h by conduit 59 (being furnished with preheater 60), height 2m) distill thus at (it is filled with Dixon filler (6mm φ)) middle part.During this distillation, the liquid from distillation tower 61 bottoms taking-up distillation tower 61.The liquid that a part is taken out is transferred to reboiler 67 by conduit 68, and then is circulated to distillation tower 61, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 61 bottoms is 116 ℃, and tower top pressure is about 13kPa, and reflux ratio is about 0.5.To be transferred to condenser 63 by conduit 62 from distillation tower 61 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 46g/h is taken out the gained condensation product continuously from condenser 63, and is transferred to pure storage tank 135 by conduit 66.Take out residual liquid the distillation tower 61 continuously from distillation tower 61 bottoms by the speed of about 155g/h, and be transferred to storage tank 69 by conduit 68.
The condensation product of collecting in storage tank 135 contains the almost 1-butanols of 100 weight % based on the weight of this condensation product, and is substantially devoid of phenol (detecting less than phenol in the analysis of condensation product).On the other hand, the residual liquid of collecting in storage tank 69 contains the dibutyl carbonate of the 5 weight % that have an appointment and the phenol of about 95 weight % based on the weight of this residual liquid.
(purifying of diaryl carbonate)
Utilize Fig. 8 and 9 shown devices, be performed as follows the purifying of diaryl carbonate.
The condensation product that to collect in storage tank 58 is sent into continuous multi-stage distillation tower 72 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 273g/h by conduit 70 (being furnished with preheater 71), distills thus.During this distillation, the liquid from distillation tower 72 bottoms taking-up distillation tower 72.The liquid that a part is taken out is transferred to reboiler 78 by conduit 79, and then is circulated to distillation tower 72, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 72 bottoms is 210 ℃, and tower top pressure is about 1.5kPa, and reflux ratio is about 1.To be transferred to condenser 74 by conduit 73 from distillation tower 72 top distillatory gases, make institute's distillatory condensation of gas thus.Take out the gained condensation product continuously and pass through conduit 77 transfers from condenser 74.Take out residual liquid the distillation tower 72 continuously from distillation tower 72 bottoms by the speed of about 27g/h, and be transferred to storage tank 80 by conduit 79.
The condensation product that takes out from conduit 77 contains the dibutyl carbonate of the 0.6 weight % that has an appointment, the carbonic acid butyl of about 34 weight % based on the weight of this condensation product. the diphenyl carbonate of phenylester and about 65 weight %.
To send into continuous multi-stage distillation tower 83 (the about 5cm of internal diameter, height 2m) (it is filled with Dixon filler (6mm φ)) middle part by the speed of about 246g/h by conduit 81 (being furnished with preheater 82) by the condensation product that conduit 77 takes out subsequently, distill thus.During this distillation, the liquid from distillation tower 83 bottoms taking-up distillation tower 83.The liquid that a part is taken out is transferred to reboiler 89 by conduit 90, and then is circulated to distillation tower 83, so that for distilling the sufficient heat of supply.This distillation is to carry out under such condition, and wherein the temperature of the liquid of distillation tower 83 bottoms is 211 ℃, and tower top pressure is about 7kPa, and reflux ratio is about 2.To be transferred to condenser 85 by conduit 84 from distillation tower 83 top distillatory gases, make institute's distillatory condensation of gas thus.Speed by about 85g/h is taken out the gained condensation product continuously from condenser 85, and is transferred to storage tank 140 by conduit 88.Take out residual liquid the distillation tower 83 continuously from distillation tower 83 bottoms by the speed of about 161g/h, and be transferred to storage tank 91 by conduit 90.
The condensation product that is transferred to storage tank 140 by conduit 88 contains the dibutyl carbonate of the 1.6 weight % that have an appointment, the carbonic acid butyl of about 98 weight % based on the weight of this condensation product. the diphenyl carbonate of phenylester and about 0.4 weight %.On the other hand, the residual liquid of collecting in storage tank 91 contains the carbonic acid butyl of the 0.2 weight % that has an appointment based on the weight of this residual liquid. the diphenyl carbonate of phenylester and about 99 weight %.
(step (1))
The liquid of will about 94g collecting in the storage tank 32 of step (2) (containing metal) is sent into the 200ml autoclave (by Toyo Koatsu Co. by conduit 24, Ltd., Japan's produce and market), this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, contain the 0.003mol dibutyl carbonate in the back complete reaction mixture that obtained in 1 hour of reaction beginning, and contain the 0.004mol dibutyl carbonate of having an appointment in the back complete reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just).
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(synthesizing of dibutyl tin two (3-methyl butanol thing))
In 1 liter of four neck flask being furnished with cooling tube (it is connected with vacuum controller and vacuum pump) and dean stark trap, 70.5g (0.28mol) dibutyltin oxide pack into (by Aldrich, U.S.A. 502g (5.7mol) 3-methyl isophthalic acid-butanols (by Aldrich, the U.S.A. produce and market) produce and market).And then, in flask, place agitator.
It is 140 ℃ oil bath that flask is immersed temperature, reduces pressure in the flask gradually to about 90kPa, the content of while stirred flask.Further reduce pressure in the flask then to 85kPa, the content of stirred flask also takes out distillate from flask simultaneously, and reacts under 85kPa and reach 12 hours, further takes out distillate simultaneously from flask.In 30 minutes, steam to remove unreacted component (for example unreacted alcohol) in the flask subsequently, reduce pressure in the flask simultaneously gradually to about 200Pa.From oil bath, take out flask, make the flask interior cooling.In flask, introduce nitrogen then, so that the pressure in the flask is risen to normal atmosphere.By this operation, obtain the 127g viscous liquid.
The distillate that analysis is taken out from flask.Found that this distillate contains the 260mmol water of having an appointment.Analyze the viscous liquid that obtains above by NMR.Found that this viscous liquid contains dibutyl tin two (3-methyl butanol thing) and 1,1,3, the 3-tetrabutyl-1,3-two (3-methyl butoxy) distannoxane.
(step (1))
The viscous liquid that 114g is obtained the above 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) of packing into, this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, carbonic acid two (3-methyl butyl) ester that contains 18mol% at the back reaction mixture that obtained in 1 hour of reaction beginning based on the molar weight of the contained tin atom of viscous liquid, mol% by carbonic acid two (3-methyl butyl) ester, and contain carbonic acid two (3-methyl butyl) ester of 20.4mol% based on the molar weight of the contained tin atom of viscous liquid at the back reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just), by the mol% of carbonic acid two (3-methyl butyl) ester.
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
After step (1), the content of autoclave is cooled to room temperature (about 20 ℃), about 6g distilled water of packing in autoclave stirred 30 minutes then, reacted thus.Stop then stirring, open autoclave.Discovery obtains white slurry in autoclave.White slurry is filtered, obtain white solid and filtrate thus.The 100ml eggplant type flask (by Okano Works, Ltd., Japanese produce and market) of being furnished with cooling tube, vacuum pump and vacuum controller filtrate packing into.And then, in flask, place agitator.Then flask is immersed temperature and is 140 ℃ oil bath.
Distill under 140 ℃, the content of stirred flask also reduces the pressure in the flask gradually simultaneously.During this distillation, water and 3-methyl isophthalic acid-butanols at first distill from flask, and carbonic acid two (3-methyl butyl) ester distills from flask then.The amount of gained carbonic acid two (3-methyl butyl) ester is about 11g.
(step (3))
In 1 liter of four neck flask being furnished with cooling tube (it is connected with vacuum controller and vacuum pump) and dean stark trap, the white solid that the top step of packing into (2) obtains and 502g (5.7mol) 3-methyl isophthalic acid-butanols (by Aldrich, the U.S.A. produce and market).And then, in flask, place agitator.
It is 140 ℃ oil bath that flask is immersed temperature, reduces pressure in the flask gradually to about 90kPa, the content of while stirred flask.Further reduce pressure in the flask then to 85kPa, the content of stirred flask also takes out distillate from flask simultaneously, and reacts under 85kPa and reach 12 hours, further takes out distillate simultaneously from flask.In 30 minutes, take out unreacted component (for example unreacted alcohol) in the flask subsequently, reduce pressure in the flask simultaneously gradually to about 200Pa.From oil bath, take out flask, make the flask interior cooling.In flask, introduce nitrogen then, so that the pressure in the flask is risen to normal atmosphere.By this operation, obtain the 112g viscous liquid.
Analyze the viscous liquid that obtains above by NMR.Found that this viscous liquid contains dibutyl tin two (3-methyl butanol thing) and 1,1,3, the 3-tetrabutyl-1,3-two (3-methyl butoxy) distannoxane.
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
To the 100ml autoclave (by Toyo Koatsu Co., Ltd., Japan's produce and market) carbonic acid two (3-methyl butyl) ester that obtains of the step above about 11g of packing into (2), 49g phenol are (by Aldrich, U.S.A. produce and market) (distillation purifying is crossed) and the catalyst A that obtains above, wherein the amount of catalyst A should make that the Pb content of gained mixture is 0.4 weight % in the autoclave.Then with autoclave sealing, and be performed as follows reaction between carbonic acid two (3-methyl butyl) ester and the phenol.With the atmosphere in the nitrogen purging autoclave.Close all valves of autoclave then, the content of beginning agitated autoclave.In autoclave, reaction is performed as follows.The internal temperature to 230 of rising autoclave ℃, the content of agitated autoclave simultaneously.Speed by 50ml/min is introduced nitrogen from autoclave base to autoclave, the valve that is positioned at autoclave top by proper handling is controlled at 100 to 200kPa scope with the internal pressure with autoclave simultaneously, distill thus and reach about 4 hours, from autoclave, to distill gaseous component.Stop subsequently introducing nitrogen, make gained reaction mixture cooling in the autoclave to autoclave.
Analyze the reaction mixture in the autoclave.Found that this reaction mixture contains the 28mmol carbonic acid two of having an appointment (3-methyl butyl) ester, about 21mmol carbonic acid 3-methyl butyl. phenylester and about 2.6mmol diphenyl carbonate.
Reaction mixture in the autoclave packed into the 100ml three-necked flask of be furnished with cooling tube (it is connected with vacuum controller and vacuum pump) and dean stark trap.And then, in flask, place agitator.Then flask is immersed temperature and is 150 ℃ oil bath.Reduce pressure in the flask gradually to about 100kPa, the content of while stirred flask reacts thus.During reaction, unreacted phenol of distillation and carbonic acid two (3-methyl butyl) ester from flask.The gained liquid reaction mixture is mainly by carbonic acid 3-methyl butyl. and phenylester and diphenyl carbonate constitute.
(step (1) of carrying out for the second time)
The viscous liquid that step above the 110g (3) the is obtained 200ml autoclave (by ToyoKoatsu Co., Ltd., Japanese produce and market) of packing into, this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, carbonic acid two (3-methyl butyl) ester that contains 18mol% at the back reaction mixture that obtained in 1 hour of reaction beginning based on the molar weight of the contained tin atom of viscous liquid, mol% by carbonic acid two (3-methyl butyl) ester, and contain carbonic acid two (3-methyl butyl) ester of 21mol% based on the molar weight of the contained tin atom of viscous liquid at the back reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just), by the mol% of carbonic acid two (3-methyl butyl) ester.
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(synthesizing of dibutyl tin two (3-methyl butanol thing))
In 1 liter of four neck flask being furnished with cooling tube (it is connected with vacuum controller and vacuum pump) and dean stark trap, 70.5g (0.28mol) dibutyltin oxide pack into (by Aldrich, U.S.A. 502g (5.7mol) 3-methyl isophthalic acid-butanols (by Aldrich, the U.S.A. produce and market) produce and market).And then, in flask, place agitator.
It is 140 ℃ oil bath that flask is immersed temperature, reduces pressure in the flask gradually to about 90kPa, the content of while stirred flask.Further reduce pressure in the flask then to 85kPa, the content of stirred flask also takes out distillate from flask simultaneously.Under 85kPa, react then and reach 12 hours, further from flask, take out distillate simultaneously.In 30 minutes, take out unreacted component (for example unreacted alcohol) in the flask subsequently, reduce pressure in the flask simultaneously gradually to about 200Pa.From oil bath, take out flask, make the flask interior cooling.In flask, introduce nitrogen then, so that the pressure in the flask is risen to normal atmosphere.By this operation, obtain the 127g viscous liquid.
Analyze distillate.Found that this distillate contains the 260mmol water of having an appointment.Analyze the viscous liquid that obtains above by NMR.Found that this viscous liquid contains dibutyl tin two (3-methyl butanol thing) and 1,1,3, the 3-tetrabutyl-1,3-two (3-methyl butoxy) distannoxane.
(step (1))
The viscous liquid that 114g is obtained the above 200ml autoclave (by Toyo Koatsu Co., Ltd., Japanese produce and market) of packing into, this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, carbonic acid two (3-methyl butyl) ester that contains 18mol% at the back reaction mixture that obtained in 1 hour of reaction beginning based on the molar weight of the contained tin atom of viscous liquid, mol% by carbonic acid two (3-methyl butyl) ester, and contain carbonic acid two (3-methyl butyl) ester of 20.4mol% based on the molar weight of the contained tin atom of viscous liquid at the back reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just), by the mol% of carbonic acid two (3-methyl butyl) ester.
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(step (2))
After step (1), the content of autoclave is cooled to room temperature (about 20 ℃), about 6g distilled water of packing in autoclave stirred 30 minutes then, reacted thus.Stop then stirring, open autoclave.Discovery obtains white slurry in autoclave.White slurry is filtered, obtain white solid and filtrate thus.The 100ml eggplant type flask (by Okano Works, Ltd., Japanese produce and market) of being furnished with cooling tube, vacuum pump and vacuum controller filtrate packing into.And then, in flask, place agitator.Then flask is immersed temperature and is 140 ℃ oil bath.
Distill under 140 ℃, the content of stirred flask also reduces the pressure in the flask gradually simultaneously.During this distillation, water and 3-methyl isophthalic acid-butanols at first distill from flask, and carbonic acid two (3-methyl butyl) ester distills from flask then.The amount of gained carbonic acid two (3-methyl butyl) ester is about 11g.
(step (3))
In 1 liter of four neck flask being furnished with cooling tube (it is connected with vacuum controller and vacuum pump) and dean stark trap, the white solid that the top step of packing into (2) obtains and 502g (5.7mol) 3-methyl isophthalic acid-butanols (by Aldrich, the U.S.A. produce and market).And then, in flask, place agitator.
It is 140 ℃ oil bath that flask is immersed temperature, reduces pressure in the flask gradually to about 90kPa, the content of while stirred flask.Further reduce pressure in the flask then to 85kPa, the content of stirred flask also takes out distillate from flask simultaneously, and reacts under 85kPa and reach 12 hours, further takes out distillate simultaneously from flask.In 30 minutes, take out unreacted component (for example unreacted alcohol) in the flask subsequently, reduce pressure in the flask simultaneously gradually to about 200Pa.From oil bath, take out flask, make the flask interior cooling.In flask, introduce nitrogen then, so that the pressure in the flask is risen to normal atmosphere.By this operation, obtain the 112g viscous liquid.
Analyze the viscous liquid that obtains above by NMR.Found that this viscous liquid contains dibutyl tin two (3-methyl butanol thing) and 1,1,3, the 3-tetrabutyl-1,3-two (3-methyl butoxy) distannoxane.
(step (4))
(Preparation of catalysts)
40g phenol and 8g yellow lead oxide are mixed together, with the gained mixture reaction vessel of packing into.Then mixture was heated 10 hours down at 180 ℃, remove the water of supervening with phenol distillation simultaneously, obtain catalyst A thus.
(production of aromatic carbonate)
To the 100ml autoclave (by Toyo Koatsu Co., Ltd., Japan's produce and market) carbonic acid two (3-methyl butyl) ester that obtains of the step above about 11g of packing into (2), 49g phenol are (by Aldrich, U.S.A. produce and market) (distillation purifying is crossed) and the catalyst A that obtains above, wherein the amount of catalyst A should make that the Pb content of gained mixture is 0.4 weight % in the autoclave.Then with autoclave sealing, and be performed as follows reaction between carbonic acid two (3-methyl butyl) ester and the phenol.With the atmosphere in the nitrogen purging autoclave.Close all valves of autoclave then, the content of beginning agitated autoclave.The internal temperature to 230 of rising autoclave ℃, the content of agitated autoclave simultaneously.Speed by 50ml/min is introduced nitrogen from autoclave base to autoclave, the valve that is positioned at autoclave top by proper handling is controlled at the internal pressure of autoclave 100 to 200kPa scope simultaneously, distill thus and reach about 4 hours, from autoclave, to distill gaseous component.Stop subsequently introducing nitrogen, make gained reaction mixture cooling in the autoclave to autoclave.
Analyze the reaction mixture in the autoclave.Found that this reaction mixture contains the 28mmol carbonic acid two of having an appointment (3-methyl butyl) ester, about 21mmol carbonic acid 3-methyl butyl. phenylester and about 2.6mmol diphenyl carbonate.
Reaction mixture in the autoclave packed into the 100ml three-necked flask of be furnished with cooling tube (it is connected with vacuum controller and vacuum pump) and dean stark trap.And then, in flask, place agitator.Then flask is immersed temperature and is 150 ℃ oil bath.Reduce pressure in the flask gradually to about 100kPa, the content of while stirred flask reacts thus.During reaction, unreacted phenol of distillation and carbonic acid two (3-methyl butyl) ester from flask.The gained liquid reaction mixture is mainly by carbonic acid 3-methyl butyl. and phenylester and diphenyl carbonate constitute.
(step (5))
After step (4), regulate flask interior pressure and oil bath temperature respectively to about 50kPa and 220 ℃, react and reach 6 hours, simultaneously stirring.During reaction, distillation carbonic acid two (3-methyl butyl) ester from flask.Analyze gained reaction mixture in the flask.Found that this reaction mixture contains the diphenyl carbonate of the 26mmol that has an appointment.
(step (1) of carrying out for the second time)
The viscous liquid that step above the 110g (3) the is obtained 200ml autoclave (by ToyoKoatsu Co., Ltd., Japanese produce and market) of packing into, this autoclave is connected with the carbon dioxide steel cylinder by SUS pipe and valve.With the autoclave sealing, with the atmosphere in the nitrogen purging autoclave.Open above-mentioned valve then, in autoclave, introduce the modulated carbon dioxide of pressure to 5MPa.Carbon dioxide is incorporated into reaches 10 minutes in the autoclave, the content of agitated autoclave simultaneously, the valve by the closing carbon dioxide gas bomb stops to introduce then.Internal temperature with autoclave rises to 120 ℃ subsequently, stirs simultaneously.React then and reach 4 hours, the internal pressure with autoclave remains about 4MPa simultaneously.
During reaction and afterwards, gather the reaction mixture sample in the autoclave and analyzing.Found that, carbonic acid two (3-methyl butyl) ester that contains 18mol% at the back reaction mixture that obtained in 1 hour of reaction beginning based on the molar weight of the contained tin atom of viscous liquid, mol% by carbonic acid two (3-methyl butyl) ester, and contain carbonic acid two (3-methyl butyl) ester of 21mol% based on the molar weight of the contained tin atom of viscous liquid at the back reaction mixture that obtained in 4 hours of reaction beginning (reaction mixture after the reaction just), by the mol% of carbonic acid two (3-methyl butyl) ester.
After the reaction, make the inner cooling of autoclave, remove carbonic acid gas wherein.
(from embodiment 4 gained dpc production hexamethylene diisocyanates)
In the 500ml flask of being furnished with agitator, thermometer and dropping funnel, diphenyl carbonate and 142g (1.5mol) phenol (by Aldrich, the U.S.A. produce and market) (distillation purifying is crossed) that the 161g (0.75mol) that packs into produces in mode substantially the same manner as Example 4.With the atmosphere in the drying nitrogen purging flask.It is 50 ℃ water-bath that flask is immersed temperature, the content of stirred flask.
After solid in confirming flask has dissolved, regulate the temperature to 45 ℃ of water-bath.Above-mentioned dropping funnel contains 35g (0.3mol) 1,6-hexanediamine (by Aldrich, the U.S.A. produce and market) (distillation purifying mistake, and remain 45 to 50 ℃).With 1 in the dropping funnel, the 6-hexanediamine splashes in the flask in about 20 minutes, to react, simultaneously with the temperature regulation of flask contents in 50 to 60 ℃ scope.
1, after being added dropwise to complete of 6-hexanediamine, further reacting and reach 1 hour, the content of stirred flask simultaneously, and be 50 ℃ by the temperature that suitable adjusting bath temperature is kept flask contents, obtain reaction mixture thus.
Analyze the gained reaction mixture by high performance liquid chromatography and gel permeation chromatography.Found that, based on 1, the molar weight of 6-hexanediamine, 1, the transformation efficiency of 6-hexanediamine is 100mol%, the productive rate of hexamethylene-bis-amino formic acid phenylester is that 99.6mol% and selectivity are 99.6mol%, and the productive rate of carbamide compound is about 0.4mol%.
The reaction mixture that obtains is above sent into continuous multi-stage distillation tower (2 inches of internal diameters, height 4m) (it is filled with Dixon filler (6mm φ)) middle part continuously by preheater, distill thus.During this distillation, take out excessive phenol from tower top with gas form, take out high boiling mixture from the tower bottom continuously with liquid form.During this distillation, making the liquid that takes out from the tower bottom is that 130 ℃ reboiler is recycled to tower by temperature, and to keep tower top pressure be about 20kPa.To be transferred to another continuous multi-stage distillation tower (2 inches of internal diameters by conduit and pump from the liquid mixture that tower bottom takes out, height 4m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, carry out the thermolysis of liquid mixture for the above 1m of this tower bottom.During this thermolysis, take out liquid from the tower bottom, making the liquid that taken out is that 220 ℃ reboiler is recycled to tower by temperature, keeping tower top pressure is about 2.6kPa.
During thermolysis, take out the mixture that contains hexamethylene diisocyanate from the part of the following 2m of cat head with gas form, take out phenol from cat head with gas form simultaneously.The mixture that will contain hexamethylene diisocyanate is sent into another continuous multi-stage distillation tower (2 inches of internal diameters, height 4m) (it is filled with Dixon filler (6mm φ)) middle part, distills, with the purifying hexamethylene diisocyanate.During distillation purifying, take out liquid from the tower bottom, making the liquid that taken out is that 120 ℃ reboiler is recycled to tower by temperature, keeping tower top pressure is about 130Pa.Analysis is from the gas of top of tower taking-up and the liquid that takes out from tower bottom.Found that the gas that takes out from top of tower is the hexamethylene diisocyanate product, its purity is 99.9 weight %, and the liquid that takes out from tower bottom mainly is made of diphenyl carbonate.
Comparative Examples 3
(from containing the dpc production hexamethylene diisocyanate of chlorine compound)
In the 500ml flask of being furnished with agitator, thermometer and dropping funnel, 161g (0.75mol) diphenyl carbonate pack into (by Bayer AG, Germany's produce and market) (it contains the hydrolyzable chlorine compound of 15 ppm by weight) and 142g (1.5mol) phenol (by Aldrich, the U.S.A. produce and market) (distillation purifying is crossed).With the atmosphere in the drying nitrogen purging flask.Then flask is immersed temperature and is 50 ℃ water-bath, the content of stirred flask.
After solid in confirming flask has dissolved, regulate the temperature to 45 ℃ of water-bath.Above-mentioned dropping funnel contains 35g (0.3mol) 1,6-hexanediamine (by Aldrich, the U.S.A. produce and market) (distillation purifying mistake, and remain 45 to 50 ℃).With 1 in the dropping funnel, the 6-hexanediamine splashes into flask in about 20 minutes, to react, simultaneously with the temperature regulation of flask contents in 50 to 60 ℃ scope.
1, after being added dropwise to complete of 6-hexanediamine, further reacting and reach 1 hour, the content of stirred flask simultaneously, and be 50 ℃ by the temperature that suitable adjusting bath temperature is kept flask contents, obtain reaction mixture thus.
Analyze the gained reaction mixture by high performance liquid chromatography and gel permeation chromatography.Found that, based on 1, the molar weight of 6-hexanediamine, 1, the transformation efficiency of 6-hexanediamine is 99mol%, the productive rate of hexamethylene-bis-amino formic acid phenylester is that 99mol% and selectivity are 99.6mol%, and the productive rate of carbamide compound is about 0.5mol%.
The reaction mixture that obtains is above sent into continuous multi-stage distillation tower (2 inches of internal diameters, height 4m) (it is filled with Dixon filler (6mm φ)) middle part continuously by preheater, distill thus.During this distillation, take out excessive phenol from tower top with gas form, take out high boiling mixture from the tower bottom continuously with liquid form.During this distillation, making the liquid that takes out from the tower bottom is that 130 ℃ reboiler is recycled to tower by temperature, and to keep tower top pressure be about 20kPa.To be transferred to another continuous multi-stage distillation tower (2 inches of internal diameters by conduit and pump from the liquid mixture that tower bottom takes out, height 4m) in (it is filled with Dixon filler (6mm φ)), send into the part of position, carry out the thermolysis of liquid mixture for the above 1m of this tower bottom.During thermolysis, take out liquid from the tower bottom, making the liquid that taken out is that 220 ℃ reboiler is recycled to tower by temperature, and to keep tower top pressure be about 2.6kPa.
Take out the mixture that contains hexamethylene diisocyanate from the part of the following 2m of top of tower with gas form, take out phenol from top of tower with gas form simultaneously.The mixture that will contain hexamethylene diisocyanate is sent into another continuous multi-stage distillation tower (2 inches of internal diameters, height 4m) (it is filled with Dixon filler (6mm φ)) middle part, distills, with the purifying hexamethylene diisocyanate.During distillation purifying, take out liquid from the tower bottom, making the liquid that taken out is that 120 ℃ reboiler is recycled to tower by temperature, and to keep tower top pressure be about 130Pa.Analysis is from the gas of top of tower taking-up and the liquid that takes out from tower bottom.Found that the gas that takes out from top of tower is the hexamethylene diisocyanate product, its purity is 99.3 weight % and contains 5ppm hydrolyzable chlorine compound, and the liquid that takes out from tower bottom mainly is made of diphenyl carbonate.
(producing polycarbonate) from embodiment 4 gained dipheryl carbonate base esters
23.5g embodiment 4 gained dipheryl carbonate base esters and 22.8g dihydroxyphenyl propane are sent into the vacuum reaction device of being furnished with agitator.(analyze dipheryl carbonate base ester by NMR, in dipheryl carbonate base ester, detect less than the impurity that contains methyl (except the methyl of the alkyl end of any compound that is present in reaction system).) subsequently, 8, carry out polyreaction under the 000Pa and reach 30 minutes, then 4, carry out polyreaction under the 000Pa and reach 90 minutes, use the atmosphere in the nitrogen purging vacuum reaction device simultaneously.Then, the temperature of vacuum reaction device context thing is risen to 270 ℃, under 270 ℃ and 70Pa, carry out further polyreaction and reach 1 hour, obtain aromatic polycarbonate thus.The gained aromatic polycarbonate is outstanding (being colourless and transparent) aspect color, and number-average molecular weight is 10,500.
Embodiment 21
(producing polycarbonate) from the dipheryl carbonate base ester that contains impurity with methyl
Between methylcarbonate and phenol, carry out transesterification reaction, obtain the carbonic acid methyl. phenylester.Making gained carbonic acid methyl. phenylester carries out disproportionation reaction, obtains dipheryl carbonate base ester products, and it contains the carbonic acid methyl of 90 ppm by weight of having an appointment. phenylester.
With 23.5g gained dipheryl carbonate base ester (contain the carbonic acid methyl. phenylester) and the 22.8g dihydroxyphenyl propane send into the vacuum reaction device of being furnished with agitator.Subsequently,, carry out polyreaction under the 000Pa and reach 30 minutes,, carry out polyreaction under the 000Pa and reach 90 minutes, use the atmosphere in the nitrogen purging vacuum reaction device simultaneously then 48.Then, the temperature of vacuum reaction device context thing is risen to 270 ℃, under 270 ℃ and 70Pa, carry out further polyreaction and reach 1 hour, obtain aromatic polycarbonate thus.The gained aromatic polycarbonate is outstanding (being colourless and transparent) aspect color, and number-average molecular weight is 9,500.
Comparative Examples 4
(producing polycarbonate) from the dipheryl carbonate base ester that contains chlorine compound
23.5g dipheryl carbonate base ester (by Bayer AG, German produce and market) (chlorine that contains 5 ppm by weight) and 22.8g dihydroxyphenyl propane are sent into the vacuum reaction device of being furnished with agitator.Subsequently,, carry out polyreaction under the 000Pa and reach 30 minutes,, carry out polyreaction under the 000Pa and reach 90 minutes, use the atmosphere in the nitrogen purging reaction unit simultaneously then 48.Then, the temperature of vacuum reaction device context thing is risen to 270 ℃, under 270 ℃ and 70Pa, carry out further polyreaction and reach 1 hour.But, can not obtain having high molecular weight polymers by above-mentioned reaction.Particularly, be 270 ℃ and 70Pa down the reaction mixtures that obtain after 1 hour of reaction only contain such mixture: it contains unreacted starting compound and number-average molecular weight is 800 or lower oligopolymer.
Industrial applicibility
The favourable part of the inventive method is that not only the method does not need to use any toxicant and do not produce any corrosive substance, but also is that the amount of accessory substance is considerably less and can recycles at the intermediate product that the production period of required aromatic carbonate produces. Thereby the inventive method is favourable for the consideration of environmental protection, can produce highly purified aromatic carbonate simple and efficiently.
Claims (37)
1, a kind of method of producing aromatic carbonate comprises:
(1) carry out reaction between organometallic compound and the carbonic acid gas, obtain containing the reaction mixture of the dialkyl carbonate that generates by this reaction,
(2) from described reaction mixture, isolate described dialkyl carbonate, obtain residual liquid, and
Partly or entirely side by side carry out the following step (3) and (4) in any order:
(3) make described residual liquid and alcohol reaction, generate at least a organometallic compound, also generate water, from described organometallic compound, remove described water and
(4) make the described dialkyl carbonate and the aromatic hydroxy compound reaction of in step (2), separating, obtain aromatic carbonate.
2, according to the process of claim 1 wherein that the described aromatic carbonate that obtains is at least a compound that is selected from carbonate alkyl aryl ester and diaryl carbonate in step (4).
3, according to the method for claim 1 or 2, wherein in step (3), will be recycled to step (1) from the described organometallic compound of wherein removing described water.
4, the method any according to claim 1 to 3 wherein in step (4), will be recycled to step (3) with the alcohol that described aromatic carbonate generates.
5, the method any according to claim 1 to 4, wherein the dialkyl carbonate that will reclaim in step (4) is recycled to step (4).
6, the method any according to claim 1 to 5, wherein the circulation with step (1) to (4) repeats at least once.
7, the method any according to claim 2 to 5, wherein the described aromatic carbonate that obtains in step (4) is a carbonate alkyl aryl ester, this method further comprises the following step (5) afterwards in step (4):
(5) described carbonate alkyl aryl ester is carried out disproportionation reaction, obtain diaryl carbonate.
8, according to the method for claim 7, wherein in step (5), will be recycled to step (4) with the dialkyl carbonate that described diaryl carbonate generates.
9, according to the method for claim 7 or 8, wherein the circulation with step (1) to (5) repeats at least once.
10, the method any according to claim 1 to 9, wherein in step (1), the consumption of described organometallic compound is 1/200 to 1 times with respect to the stoichiometric quantity of the amount of described carbonic acid gas.
11, the method any according to claim 1 to 10, wherein described in the step (1) is reflected under 20 ℃ or the higher temperature and carries out.
12, the method any according to claim 1 to 11, wherein the described organometallic compound that uses in step (1) is the organometallic compound with metal-oxygen-carbon key.
13, according to the method for claim 12, the described organometallic compound that wherein has the metal-oxygen-carbon key comprises at least a following compound that is selected from:
Organometallic compound by formula (1) representative:
Wherein:
M
1Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families, except the silicon;
Each R
1And R
2Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl, by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl is perhaps represented the C that does not replace or replace
6-C
20Aryl;
Each R
3And R
4Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl or by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl; With
Each a and b are 0 to 2 integers, and a+b=0 to 2, each c and d are 0 to 4 integers, and a+b+c+d=4; And
Organometallic compound by formula (2) representative:
Wherein:
Each M
2And M
3Representative is selected from the atoms metal of the element that belongs to periodictable the 4th and 14 families independently, except the silicon;
Each R
5, R
6, R
7And R
8Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl, by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl is perhaps represented the C that does not replace or replace
6-C
20Aryl;
Each R
9And R
10Represent straight or branched C independently
1-C
12Alkyl, C
5-C
12Cycloalkyl, straight or branched C
2-C
12Thiazolinyl or by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20Aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl; With
Each e, f, g and h are 0 to 2 integers, e+f=0 to 2, and g+h=0 to 2, each i and j are 1 to 3 integers, e+f+i=3, and g+h+j=3.
14, the method any according to claim 1 to 13, wherein the described separation of dialkyl carbonate described in the step (2) is undertaken by at least a distillation, extraction and the filtering separation method of being selected from.
15, according to the method for claim 14, wherein the described separation of dialkyl carbonate is undertaken by distillation described in the step (2).
16, according to the method for claim 15, wherein the described separation of dialkyl carbonate is undertaken by thin film distillation described in the step (2).
17, the method any according to claim 1 to 16, wherein described the removing by membrane sepn of water described in the step (3) carried out.
18, according to the method for claim 17, wherein said membrane sepn is a pervaporation.
19, the method any according to claim 1 to 16, wherein described the removing by distillation of water described in the step (3) carried out.
20, the method any according to claim 1 to 19, wherein the described alcohol that uses in step (3) is at least a following alcohol that is selected from: have straight or branched C
1-C
12The alkyl alcohol of alkyl, has C
5-C
12The cycloalkyl alcohol of cycloalkyl, has straight or branched C
2-C
12The alkenyl alcohol of thiazolinyl and having by the C that does not replace or replace
6-C
19The C that aryl and alkyl constitute
7-C
20The aralkyl alcohol of aralkyl, described alkyl is selected from straight or branched C
1-C
14Alkyl and C
5-C
14Cycloalkyl.
21, the method any according to claim 1 to 20, wherein the boiling point of the alcohol that uses in step (3) is higher than the boiling point of water.
22, according to the method for claim 21, wherein the alcohol that uses in step (3) is at least a following alcohol that is selected from: 1-butanols, 2-methyl isophthalic acid-propyl alcohol, have straight or branched C
5-C
12The alkyl alcohol of alkyl and have a straight or branched C
4-C
12The alkenyl alcohol of thiazolinyl.
23, according to the method for claim 21 or 22, wherein the boiling point of the alcohol that uses in step (3) is lower than the boiling point of the described aromatic hydroxy compound that uses in step (4).
24, according to the method for claim 13, the R in its Chinese style (1)
3And R
4And the R in the formula (2)
9And R
10In each represent normal-butyl, 2-methyl-propyl, straight or branched C independently
5-C
12Alkyl or side chain C
4-C
12Thiazolinyl.
25, the method any according to claim 1 to 24, wherein in step (1), described organometallic compound uses with at least a form that is selected from monomeric form, oligomeric form, polymerized form and association form.
26, according to claim 13,24 and 25 any one methods, the M in its Chinese style (1)
1And the M in the formula (2)
2And M
3In each represent tin atom.
27, the method any according to claim 1 to 26, wherein the described organometallic compound that uses in step (1) is by organotin oxides and alcohol preparation.
28, the method any according to claim 1 to 27, wherein the amount of the described aromatic hydroxy compound that uses in step (4) is with respect to the stoichiometric quantity of the amount of the described dialkyl carbonate of use in step (4) 0.1 to 10,000 times.
29, the method any according to claim 1 to 28, wherein described in the step (4) is reflected under 50 to 350 ℃ the temperature and carries out.
30, the method any according to claim 1 to 29, wherein described in the step (4) is reflected under the existence of catalyst for ester exchange reaction and carries out.
31, the method any according to claim 7 to 30, wherein described in the step (5) is reflected under the existence of disproportionation reaction catalyzer and carries out.
32, the method any according to claim 1 to 31, wherein said aromatic hydroxy compound is represented by following formula (3):
ArOH (3)
Wherein Ar is C
5-C
30Aromatic group.
33, according to the method for claim 32, wherein the described aromatic hydroxy compound by formula (3) representative is a phenol.
34, the method any according to claim 1 to 33, wherein the total content in the described alcohol that uses in step (3) of aromatic hydroxy compound and carboxylated compound is 1,000ppm or lower.
35, the aromatic carbonate of producing by any one method of claim 1 to 34.
36, use polycarbonate, isocyanic ester or the polycarbonate diol of the aromatic carbonate production of claim 35.
37, according to polycarbonate, isocyanic ester or the polycarbonate diol of claim 36, wherein said aromatic carbonate is a diaryl carbonate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP185078/2003 | 2003-06-27 | ||
| JP2003185077 | 2003-06-27 | ||
| JP185077/2003 | 2003-06-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1839112A true CN1839112A (en) | 2006-09-27 |
| CN100453520C CN100453520C (en) | 2009-01-21 |
Family
ID=37016143
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800241943A Expired - Lifetime CN100453520C (en) | 2003-06-27 | 2004-06-25 | Method for producing aromatic carbonate |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100453520C (en) |
| ES (1) | ES2367797T3 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186806B (en) * | 2008-12-01 | 2015-01-28 | 国际壳牌研究有限公司 | Process for removing an alkanol impurity from an organic carbonate stream |
| TWI496763B (en) * | 2008-05-15 | 2015-08-21 | Asahi Kasei Chemicals Corp | Preparation of isocyanates |
| CN105612143A (en) * | 2013-10-02 | 2016-05-25 | 三星Sdi株式会社 | Method for preparing aromatic carbonate |
| CN106999924A (en) * | 2014-12-04 | 2017-08-01 | 国际壳牌研究有限公司 | Aromatic carbonate prepares the manufacture method of catalyst |
| CN113166030A (en) * | 2018-12-07 | 2021-07-23 | 三菱瓦斯化学株式会社 | Process for producing dialkyl carbonate |
| CN114555553A (en) * | 2019-10-03 | 2022-05-27 | 国际壳牌研究有限公司 | Process for the preparation of dialkyl carbonates and alkanediols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791234B2 (en) * | 1990-12-26 | 1995-10-04 | 旭化成工業株式会社 | Continuous production of aromatic carbonates |
| JPH05331108A (en) * | 1992-06-01 | 1993-12-14 | Mitsubishi Gas Chem Co Inc | Production of aromatic carbonic acid ester |
-
2004
- 2004-06-25 ES ES04746852T patent/ES2367797T3/en not_active Expired - Lifetime
- 2004-06-25 CN CNB2004800241943A patent/CN100453520C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI496763B (en) * | 2008-05-15 | 2015-08-21 | Asahi Kasei Chemicals Corp | Preparation of isocyanates |
| CN102186806B (en) * | 2008-12-01 | 2015-01-28 | 国际壳牌研究有限公司 | Process for removing an alkanol impurity from an organic carbonate stream |
| CN105612143A (en) * | 2013-10-02 | 2016-05-25 | 三星Sdi株式会社 | Method for preparing aromatic carbonate |
| US9765013B2 (en) | 2013-10-02 | 2017-09-19 | Lotte Advanced Materials Co., Ltd. | Method for preparing aromatic carbonate |
| CN105612143B (en) * | 2013-10-02 | 2018-05-08 | 乐天尖端材料株式会社 | The method for preparing aromatic carbonate |
| CN106999924A (en) * | 2014-12-04 | 2017-08-01 | 国际壳牌研究有限公司 | Aromatic carbonate prepares the manufacture method of catalyst |
| CN106999924B (en) * | 2014-12-04 | 2019-11-29 | 国际壳牌研究有限公司 | Aromatic carbonate prepares the manufacturing method of catalyst |
| CN113166030A (en) * | 2018-12-07 | 2021-07-23 | 三菱瓦斯化学株式会社 | Process for producing dialkyl carbonate |
| CN113166030B (en) * | 2018-12-07 | 2024-03-19 | 三菱瓦斯化学株式会社 | Process for producing dialkyl carbonate |
| CN114555553A (en) * | 2019-10-03 | 2022-05-27 | 国际壳牌研究有限公司 | Process for the preparation of dialkyl carbonates and alkanediols |
| CN114555553B (en) * | 2019-10-03 | 2024-04-05 | 国际壳牌研究有限公司 | Process for preparing dialkyl carbonates and alkanediols |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2367797T3 (en) | 2011-11-08 |
| CN100453520C (en) | 2009-01-21 |
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