CN101195095B - Organic acid base catalyst for synthesizing aryl ester carboxylic acid by interesterification - Google Patents
Organic acid base catalyst for synthesizing aryl ester carboxylic acid by interesterification Download PDFInfo
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Abstract
The invention belongs to the technical fields of organic chemistry and catalytic chemistry, and relates to an organic acid-base catalyst which is used for carboxylic acid aryl-ester groups which are compounded by ester exchanges. The organic base in the organic acid-base catalyst refers to an organic compound which contains nitrogen, phosphorus and halogen elements and solid-carrying organic base of the organic base, while the organic acid mainly refers to organic sulfonic acid, organic phosphorus acid, organic carboxyl acid, urea and the like and solid-carrying organic acid of the organic acid. The invention can be used as organic matters such as amino acid and the like which has double functions of organic acid and base and as catalysts which can be used to solid support the organic acid base on a same carrier. The catalyst of the invention has good catalytic performance and is easy to be separated from reaction systems, ester exchange conditions are temperate, the invention is convenient to continue, the conversion rate of oxalic dim-ethyl ester can reach over 90%, the selectivity to phenyloxalate can reach over 70%, and the invention is suitable for industry applications.
Description
Technical field
The invention belongs to organic chemistry and technical field of catalysis chemistry, relate to the organic acids and base catalyst that a class is used for carboxylic acid dialkyl esters and single aromatic hydroxy compound ester exchange synthesis of carboxylic acid list aryl ester and diaryl carboxylate.
Background technology
Diaryl carbonate is little, the free of contamination important organic carbonate of a kind of toxicity, can be used for synthetic many important organic compounds and macromolecular material, be mainly used in and bisphenol-A (2,2-two p-hydroxybenzene propane) reaction, the non-phosgene ester exchange polycondensation synthesizes high-quality Merlon, has very high economic worth.The synthetic method of diaryl carbonate mainly contains phosgenation, ester-interchange method and single aromatic hydroxy compound oxidative carbonylation method etc.Traditional diaryl carbonate synthesis technique uses phosgenation, but the phosgene severe toxicity that phosgenation uses, and be difficult for transportation, and accessory substance HCl corrosivity is strong, and environmental pollution is serious, and this method just progressively is eliminated.Single aromatic hydroxy compound oxidative carbonylation method combined coefficient is not high, and the catalyst costliness.Ester-interchange method adopts a kind of single aromatic hydroxy compound (for example phenol, methylphenol, xylenol etc.) and a kind of carboxylic acid dialkyl esters (for example dimethyl carbonate, dimethyl oxalate, diethyl carbonate, diethy-aceto oxalate etc.) to carry out ester exchange reaction and generates diaryl carboxylate.This method is a kind of eco-friendly method, and it has avoided employed harmful substance in the traditional handicraft, as phosgene, METHYLENE CHLORIDE etc.Ester-interchange method mainly comprises phenol and dimethyl carbonate ester-interchange method, phenol and dimethyl oxalate ester-interchange method.The catalyst that is adopted mainly contains homogeneous phase and heterogeneous two big classes.
Phenol and the research of dimethyl carbonate synthesis of diphenyl carbonate by ester exchange reaction method are more in the ester-interchange method, as JP323654, US5426207, DE2528142, CN1803282 patents such as (200610020205.1) is reported, the material carbon dimethyl phthalate that uses in the method cheaply is easy to get, and the problem that this technology exists is that methyl alcohol and dimethyl carbonate form azeotropic mixture, have increased the separating difficulty of raw material and product; Reaction rate is slow excessively, the production operation excessive cycle.
In dimethyl oxalate and the phenol ester exchange synthesizing diphenyl carbonate technology, the raw material dimethyl oxalate can be synthetic by the oxidization of methanol carbonylation, shown in reaction (1), dimethyl oxalate and phenol ester exchange the synthesis of oxalic acid diphenyl ester then, as reaction (2), phenostal decarbonylation base prepares diphenyl carbonate afterwards, and shown in reaction (3), the yield of de-carbonyl reaction is greater than 95%.By-product carbinol is easy to separate from reaction system with carbon monoxide in this method, avoided adopting the problem of by-product carbinol and material carbon dimethyl phthalate formation azeotropic in dimethyl carbonate and the phenol ester exchange synthesizing diphenyl carbonate technology, reduced separating difficulty, methyl alcohol and carbon monoxide can pass through oxidative carbonylation method synthesizing dimethyl oxalate again, realize Atom economy.Simultaneously, adopt synthesis under normal pressure, the reaction condition gentleness, catalyst also cheaply is easy to get than the synthesizing diphenyl carbonate from phenol oxidation carbonylation method, so be a rising process route.
The prior art close with the present invention is that phenol and dimethyl oxalate ester exchange reaction generate phenostal, in the course of reaction, phenol and dimethyl oxalate at first ester exchange generate methyl phenyl oxalate, methyl phenyl oxalate continues ester exchange or disproportionated reaction takes place self to generate phenostal more then, experiences following reactions steps:
With this key technology is that the dpc production technology of core occurred in the nineties, the Ube company of Japan is devoted to the research of this respect always, and applied for many patents, as EP1013633A1, US5731453, US5811573, US5834615, EP0832872A1, US5922827 etc.In above-mentioned patent, relating to the dimethyl oxalate is raw material prepares diphenyl carbonate synthesis by ester exchange raw material, when being phenostal, used ester exchange catalyst can be the organic acid compound of alkali metal, cadmium, zirconium, lead, iron, copper, zinc compound or organo-tin compound, aluminium, titanium, vanadium etc., but be the homogeneous catalyst that dissolves in reaction system, all used complicated piece-rate system or equipment that catalyst is separated with reaction system.Recently, people such as domestic Ma Xinbin have studied a series of load metal oxide heterogeneous catalysts, and applied for many patents, as CN200410018842.6, CN200410018843.0, CN200410019329.9, CN200410019331.6, CN200410019332.0, CN200410019333.5, CN200610016188.4 etc.In above-mentioned patent, with the dimethyl oxalate is raw material prepares diphenyl carbonate synthesis by ester exchange raw material, when being methyl phenyl oxalate or phenostal, used catalyst has load type titania, compound amorphous ti silica, the support type molybdenum trioxide, support type Mo-Sn bimetallic oxide etc., these catalyst all are weak Lewis acid catalysts, when in batch reactor, reacting, activity of such catalysts and not high to the selectivity of principal product phenostal, particularly the selectivity of phenostal is all less than 47.5%, and the activated centre metal ion in the heterogeneous catalyst easily is lost in the reaction mass in ester exchange reaction.
Summary of the invention
The object of the present invention is to provide the organic acids and base catalyst of a class catalysis synthesizing aryl ester carboxylic acid.
For achieving the above object, the present invention is realized by following technical proposals.
A kind of organic acids and base catalyst that is used for the ester exchange synthesizing aryl ester carboxylic acid comprises the catalyst that organic alkali catalyst, organic acid catalyst, organic acids and base bifunctional catalyst or silane reagent are handled in the catalyst; Described organic base is the organic compound and the supported organic base thereof of nitrogenous, phosphorus or halogens; Described organic acid is organic sulfonic acid, organic phosphoric acid, organic carboxyl acid and carbamide compounds and supported organic acid thereof; Described organic acids and base bifunctional catalyst is an amino acids or with the immobilized catalyst on identical carrier of organic acids and base, and the catalyst that described silane reagent is handled is that the surface hydroxyl with supported heterogeneous catalyst carries out the catalyst that silane reagent is handled.
It is the surface hydroxyl of supported heterogeneous catalyst to be carried out the silane reagent processing of opposed polarity that silane reagent is handled, thereby obtains the different catalyst of surface polarity.
The above-mentioned organic acids and base catalyst that is used for the ester exchange synthesizing aryl ester carboxylic acid, described organic alkali catalyst is to comprise aniline, methylphenylamine, N, accelerine, octadecylamine, trioctylamine, cyclohexylamine, benzylamine, proline, pyridine, pyrazoles bipyridyl, acetylpyridine, 2, compound and supported organic bases thereof such as 2 '-bipyridyl, quinoline, pyrazoles, imidazoles, adenine, phenanthroline, triphenylphosphine; Described organic acid catalyst is to comprise compound and supported organic acids thereof such as benzene sulfonic acid, propyl sulfonic acid.
The above-mentioned organic acids and base catalyst that is used for the ester exchange synthesizing aryl ester carboxylic acid, described supported carrier is to contain silicon carrier, comprises mesopore molecular sieve MCM-41, mesoporous molecular sieve SBA-15, silica gel, compound titanium silicalite material, compound molybdenum silicon materials.
The organic acids and base Application of Catalyst that is used for the ester exchange synthesizing aryl ester carboxylic acid of the present invention is to be starting ester exchange process synthesis of carboxylic acid list aryl ester or diaryl carboxylate with carboxylic acid dialkyl esters and single aromatic hydroxy compound.
Described carboxylic acid dialkyl esters is dimethyl oxalate, diethy-aceto oxalate, dimethyl carbonate or diethyl carbonate; Described single aromatic hydroxy compound is phenol, methylphenol or xylenol; Described carboxylic acid list aryl ester is methyl aryl oxalate, ethyl aryl oxalate, methyl aryl carbonic ester or ethyl aryl carbonates; Described diaryl carboxylate is diaryl esters of oxalic acid or diaryl carbonate.
The organic acids and base catalyst is used for the application of ester exchange synthesizing aryl ester carboxylic acid, concrete course of reaction and reaction condition are: in the reactor of rectifying column is housed, with dimethyl oxalate and phenol is raw material, raw materials components mole ratio dimethyl oxalate: phenol=20: 1～400, reaction time is 1～20 hour, and reaction temperature is 160～240 ℃, and spontaneous reaction pressure is 0～1.0MPa, under the organic acids and base catalyst action, generate phenostal or/and methyl phenyl oxalate; The consumption of heterogeneous catalyst and the mass ratio of total feed are 1/5000～1/16, and the mol ratio of homogeneous catalyst and total feed is 1/10000～1/10.
Under above-mentioned reaction condition, be equipped with in the course of reaction of carrying out in the reactor of rectifying column and can in reactor, feed 5～10000ml/min nitrogen or argon gas, make the selectivity and the yield of end product phenostal can reach 74% and 73% respectively, and product methyl alcohol and methyl phenyl ethers anisole steam reactor with nitrogen or argon gas in course of reaction, only contain reactant, oxalic acid benzene methyl and phenostal in the reactor, the product separation process is simplified.The gas flow preferable range is 10～100ml/min.
This method is when using homogeneous phase organic acids and base (particularly nitrogenous organic base) as catalyst, the conversion ratio height of dimethyl oxalate not only, the selectivity of oxalic acid benzene methyl and phenostal is also higher, especially the more metallic chemical combination object height of the selectivity of phenostal.During homogeneous reaction, the molar content that catalyst amount accounts for reaction system is 0.2% and has catalytic performance preferably when (be ten of the homogeneous catalyst consumption reported /once), still kept catalytic effect preferably, and catalyst separation is simple, has save the losing issue of metal ion.And the supported heterogeneous catalyst of organic acids and base had both kept the catalytic performance of homogeneous catalyst, had save complex separations technology and equipment to catalyst again.Therefore, this technical process is simply efficient.
The invention has the advantages that, the operating condition gentleness, the reaction time is short, catalyst performance good, catalyst easily separates with reaction system, whole reaction system is convenient to realize serialization, the dimethyl oxalate conversion ratio can reach more than 90%, the phenostal selectivity can reach 70%, is applicable to industrial applications.Prepared phenostal can be used for diphenyl carbonate synthesis.
The specific embodiment
Below by specific embodiment the present invention is further specified, but do not limited the present invention.
[embodiment 1]
Embodiments of the invention are with under catalyst reaction condition of the present invention, are that feedstock production methyl phenyl oxalate and phenostal are that example is investigated with dimethyl oxalate and phenol, and course of reaction is identical with (4)-(6) reactions steps in the background technology.
Detailed process is, carries out in the there-necked flask of 100ml, and the heating of heat collecting type electromagnetic agitation is furnished with thermometer, to show temperature of reaction system.The consumption of technical grade dimethyl oxalate is 17 mMs, and the consumption of analyzing purified petroleum benzin phenol is 85 mMs, 0.3 gram Cp ' (CH
2)
3-MCM-41 is heterogeneous catalyst (containing luxuriant 0.38 mM in the 0.3 gram catalyst), adds under normal pressure.Stir and heat up, reaction temperature is controlled at 180 ± 2 ℃, and the reaction time is 2 hours.(4)-(6) reaction equilibrium constant of reactions steps is all minimum, for breaking the restriction of thermodynamical equilibrium, improve conversion of raw material, flask is equipped with the reflux condensing tube of feeding a little more than the thermostatical circulating water of the boiling point (as 80 ℃) of methyl alcohol, the methyl alcohol that reaction generates can constantly steam from the reactant mixture system, and collects distillate in cold well.With gas-chromatography reaction result is analyzed.Selectivity and yield with the conversion ratio of DMO (dimethyl oxalate), AN (methyl phenyl ethers anisole), MPO (oxalic acid benzene methyl), DPO (phenostal) are index, investigate reactivity worth, see Table 1.
[embodiment 2-5]
With immobilized luxuriant ring material Cp ' (CH on Si-MCM-41
2)
3-MCM-41 is a heterogeneous catalyst, catalyst amount is 0.3 gram (containing luxuriant 0.38 mM in the 0.3 gram catalyst), and the reaction time carried out respectively 4,6,8,10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 2-5, investigate reaction result.
Table 1:Cp ' (CH
2)
3Reaction evaluating when-MCM-41 is catalyst
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | ?DPO | ||
| 1 2 3 4 5 | 2 4 6 8 10 | 38.0 77.0 79.4 83.4 89.9 | 4.8 1.2 2.5 2.8 1.0 | 84.3 70.3 65.8 58.4 52.8 | 9.2 28.5 31.7 38.8 46.2 | 1.8 0 0 0 0 | 32.1 54.1 52.3 48.7 47.5 | 3.5 22.0 25.1 32.3 41.5 |
[embodiment 6-10]
With 0.38 mM Cp ' (CH
2)
3-MCM-41 is a homogeneous catalyst, catalyst amount is 0.38 mM, and the reaction time carried out respectively 2,4,6,8,10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 6-10, investigate reaction result.
Table 2:Cp ' (CH
2)
3Si (OEt)
3Reaction evaluating during for catalyst
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 6 7 8 9 10 | 2 4 6 8 10 | 40.3 70.4 86.4 95.0 97.5 | 5.8 15.3 25.4 36.9 54.1 | 79.1 60.9 44.7 28.2 15.8 | 10.2 21.9 28.4 32.5 27.9 | 4.8 2.0 1.5 2.4 2.2 | 31.9 42.9 38.6 26.8 15.4 | 4.1 15.4 24.6 30.9 27.2 |
Comparative example 1-5 and 6-10 are as can be known, not only help reaction mass and catalyst separation after luxuriant ring is immobilized, and keeping catalyst activity to change under the little situation, and catalyst improves the overall selectivity of principal product MPO and DPO, and particularly the selectivity to end product DPO improves.Among the embodiment 5, in the time of 10 hours, the yield of phenostal reaches 41.5% in reaction.
[embodiment 11-14]
With immobilized luxuriant ring material Cp ' (CH on Si-MCM-41
2)
3-MCM-41 is a heterogeneous catalyst, and catalyst reacts coreaction again through simple washing drying and (has loss in the catalyst recovery process 4 times, the consumption of respective reaction thing by with the catalyst consumption quality than decrement), and the reaction time is 10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 11-14, investigate reaction result.
Table 3:Cp ' (CH
2)
3The estimation of stability of-MCM-41 catalyst
| Embodiment | Reaction times (inferior) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | DPO | ||
| 11 12 13 14 | 1 2 3 4 | 89.9 81.6 75.8 63.9 | 1.0 0.6 1.9 0.7 | 52.8 64.1 67.1 75.7 | 46.2 35.3 30.3 23.1 | 0 0 0.7 0.5 | 47.5 52.3 50.8 48.4 | 41.5 28.8 22.9 14.8 |
By embodiment 11-14 as can be known, Cp ' (CH
2)
3-MCM-41 catalyst is when catalysis dimethyl oxalate and phenol ester exchange reaction, and catalyst is along with the increase of reaction times, and the selectivity of reactivity and DPO reduces gradually.
[embodiment 15-18]
With Cp ' (CH
2)
3-MCM-41 is a heterogeneous catalyst with the alkylating material of HMDS, and catalyst reacts coreaction again through simple washing drying and (has loss in the catalyst recovery process 4 times, the consumption of respective reaction thing by with catalyst consumption than decrement), and the reaction time is 10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 15-18, investigate reaction result.
Table 4: the Cp ' (CH behind the silanization
2)
3The estimation of stability of-MCM-41 catalyst
| Embodiment | Reaction times (inferior) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | ?MPO | ?DPO | Other | MPO | DPO | ||
| 15 16 17 18 | 1 2 3 4 | 78.8 83.9 84.2 71.3 | 1.9 1.2 0.4 0.2 | 64.4 60.7 60.3 64.9 | 33.7 38.2 39.3 34.3 | 0 0 0 0.6 | 50.8 50.9 50.8 46.3 | 26.5 32.0 33.1 24.5 |
Comparative example 11-14 and embodiment 15-18 as can be known, Cp ' (CH
2)
3The catalyst of-MCM-41 silanization is when catalysis dimethyl oxalate and phenol ester exchange reaction, catalyst reacts coreaction 4 times again through simple washing drying, the selectivity of reactivity and DPO changes little, catalyst stability is better than the stability of the catalyst before the silanization, and catalyst can carry out repeatedly recycling by simple washing drying.
[embodiment 19-21]
With 0.3 gram NH
2(CH
2)
3-MCM-41 (contains-NH in the 0.3 gram catalyst
20.7 mM) be heterogeneous catalyst, and the reaction time carried out respectively 2,6,10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 19-21, investigate reaction result.
Table 5:NH
2(CH
2)
3Reaction evaluating when-MCM-41 is catalyst
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | DPO | ||
| 19 20 21 | 2 6 10 | 5.7 75.5 95.3 | 5.8 3.9 10.7 | 88.4 68.8 58.6 | 5.9 27.2 30.7 | 0 0 0 | 4.9 52.0 55.8 | 0.3 20.6 29.2 |
[embodiment 22-24]
With 0.7 mM NH
2(CH
2)
3Si (OEt)
3Be homogeneous catalyst, and the reaction time carried out respectively 2,6,10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 22-24, investigate reaction result.
Table 6:NH
2(CH
2)
3Si (OEt)
3Reaction evaluating during for catalyst
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | ?AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 22 23 24 | 2 6 10 | 10.4 59.9 83.6 | ?12.6?6.5?9.9 | ?85.8?76.0?56.8 | 1.6 17.5 33.3 | 0 0 0 | 8.9 45.6 47.5 | 0.2 10.5 27.8 |
Comparative example 19-21 and 22-24 not only help reaction mass and catalyst separation after propylamine is immobilized as can be known, and are keeping catalyst performance to be better than corresponding homogeneous catalyst NH
2(CH
2)
3Si (OEt)
3, catalyst improves the overall selectivity of principal product MPO and DPO, and particularly the selectivity to end product DPO improves.Among the embodiment 21, in the time of 10 hours, the yield of phenostal reaches 29.2% in reaction.
[embodiment 25-30]
With 0.3 gram NH
2(CH
2)
3-MCM-41 (contains-NH in the 0.3 gram catalyst
20.7 mM) be heterogeneous catalyst, and catalyst reacts coreaction again through simple washing drying and (has loss in the catalyst recovery process 6 times, the consumption of respective reaction thing by with catalyst consumption than decrement), and the reaction time is 10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 25-30, investigate reaction result.
Table 7:NH
2(CH
2)
3The estimation of stability of-MCM-41
| Embodiment | Reaction times (inferior) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | DPO | ||
| 25 26 27 28 29 30 | 1 2 3 4 5 6 | 95.3 80.5 88.4 87.8 88.9 87.7 | 10.7 5.0 3.3 2.7 2.2 1.7 | 58.6 60.4 50.4 49.9 52.0 52.3 | 30.7 34.6 45.8 47.3 45.8 46.0 | 0 0 0.5 0 0 0.1 | 55.8 48.6 44.6 43.9 46.2 45.9 | 29.2 27.9 40.5 41.6 40.7 40.3 |
By embodiment 25-30 as can be known, NH
2(CH
2)
3-MCM-41 catalyst has kept the stability of catalyst when catalysis dimethyl oxalate and phenol ester exchange reaction, catalyst can carry out repeatedly recycling by simple washing drying.
[embodiment 31-35]
With 3-(2-pyridine radicals) pyrazoles is homogeneous catalyst, change the consumption of 3-(2-pyridine radicals) pyrazoles, be respectively 0,2,10,20,40 milligrams, and the reaction time be 10 hours, under other condition and embodiment 1 identical condition, carry out ester exchange reaction, form embodiment 31-35 respectively, investigate reaction result.
Table 8:3-(2-pyridine radicals) pyrazoles catalyzed transesterification result
| Embodiment | Catalyst (mM) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | ?MPO | DPO | Other | MPO | ?DPO | ||
| 31 32 33 34 35 | 0 0.0137 0.0686 0.1371 0.2742 | 6.9 58.4 80.4 97.2 98.9 | 2.3 2.9 12.3 21.7 66.4 | 93.3 77.8 56.5 28.5 8.9 | 1.4 19.3 31.2 49.0 22.1 | 3.0 0.0 0.0 0.9 2.5 | 6.4 45.5 45.4 27.7 8.8 | 0.1 11.2 25.1 47.6 21.9 |
By embodiment 34 as can be known, 3-(2-pyridine radicals) pyrazoles catalyst is when catalysis dimethyl oxalate and phenol ester exchange reaction, under other condition and embodiment 1 identical condition, when catalyst consumption was 0.1371 mM, the yield of DPO reached maximum 47.6%.
[embodiment 36]
Under 30ml/min nitrogen or argon gas drive, with 3-(2-pyridine radicals) pyrazoles is homogeneous catalyst, the consumption of 3-(2-pyridine radicals) pyrazoles is 0.1371 mM, reaction time is 10 hours, under other condition and embodiment 1 identical condition, carry out ester exchange reaction, form embodiment 36, investigate reaction result.
Described nitrogen or argon gas drive down, are to make to be reflected to carry out in the reactor that rectifying column is housed, and feed 30ml/min nitrogen or argon gas in the course of reaction in reactor.
Table 9:3-(2-pyridine radicals) pyrazoles catalyzed transesterification result
| Embodiment | Catalyst (mM) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | DPO | ||
| 36 | 0.1371 | 98.7 | 9.1 | 16.2 | 74.2 | 0.0 | 16.0 | 73.2 |
Comparative example 34 and 36 as can be known, 3-(2-pyridine radicals) pyrazoles catalyst is when catalysis dimethyl oxalate and phenol ester exchange reaction, the methyl alcohol that feeding 30ml/min nitrogen or argon gas are taken away the reaction generation speeds up, cause reaction speed to be accelerated, the selectivity that the employing of the method makes principal product DPO brings up to 73.2% from 49.0%, thereby makes the yield of DPO reach 73.2%.
The flow velocity that feeds nitrogen or argon gas in reactor is not limited to 30ml/min, can be within 5～10000ml/min scope.The test explanation, nitrogen or argon gas flow velocity preferable range are 10-100ml/min.
[embodiment 37-41]
(contain 2 milligrams of 3-(2-pyridine radicals) pyrazoles in the 0.3 gram catalyst with 0.3 gram 3-(2-pyridine radicals) pyrazoles silicon-based hybrid material P, i.e. 0.14 mM) be heterogeneous catalyst, and the reaction time carried out respectively 2,4,6,8,10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 37-41, investigate reaction result.
Table 10:3-(2-pyridine radicals) pyrazoles silicon-based hybrid material P catalyzed transesterification result
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 37 38 39 40 41 | 2 4 6 8 10 | 43.1 57.3 78.3 91.3 93.1 | 22.2 22.7 7.5 7.5 10.4 | 68.4 65.9 56.0 44.4 38.7 | 9.4 11.4 36.6 48.3 50.4 | 0.0 0.0 0.0 0.1 0.6 | 29.5 37.8 43.8 40.5 36.0 | 4.0 6.5 28.6 44.0 46.9 |
Comparative example 34 and 41 as can be known, 3-(2-pyridine radicals) not only helps reaction mass and catalyst separation after pyrazoles is immobilized, catalyst improves the overall selectivity of principal product MPO and DPO.Among the embodiment 41, reaction 10 hours, the yield of phenostal reached 46.9%.
[embodiment 42-46]
Under 30ml/min nitrogen or argon gas drive, with 0.3 gram 3-(2-pyridine radicals) pyrazoles silicon-based hybrid material P is heterogeneous catalyst, and the reaction time carried out respectively 2,4,6,8,10 hours, under other condition and embodiment 1 identical condition, carry out ester exchange reaction, form embodiment 42-46, investigate reaction result.
Table 11:3-(2-pyridine radicals) pyrazoles silicon-based hybrid material P catalyzed transesterification result
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | ?DPO | ||
| 42 43 44 45 46 | 2 4 6 8 10 | 68.3 80.3 90.8 96.8 99.1 | 13.7 8.4 12.2 5.0 2.2 | 66.0 59.1 43.4 28.9 23.4 | 20.2 32.5 44.4 65.1 73.1 | 0.1 0.0 0.0 1.0 1.4 | 45.1 47.4 39.4 28.0 23.2 | 13.8 26.1 40.3 63.0 72.4 |
Comparative example 37-41 and 42-46 are as can be known, supported 3-(2-pyridine radicals) pyrazoles catalyst is when catalysis dimethyl oxalate and phenol ester exchange reaction, the methyl alcohol that feeding 30ml/min nitrogen or argon gas are taken away the reaction generation speeds up, cause reaction speed to be accelerated, the selectivity that the employing of the method makes principal product DPO brings up to 73.1% from 50.4%, thereby makes the yield of DPO reach 72.4%.
[embodiment 47-52]
Silicon-based hybrid material C with 0.3 gram 3-(2-pyridine radicals) pyrazoles and chloropropyl silane graft is a heterogeneous catalyst, and the reaction time carried out respectively 2,4,6,8,10,12 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 47-52, investigate reaction result.
The silicon-based hybrid material catalyzed transesterification knot of table 12:3-(2-pyridine radicals) pyrazoles and chloropropyl silane graft
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | ?DPO | ||
| 47 48 49 50 51 52 | 2 4 6 8 10 12 | 34.1 58.0 74.5 82.9 87.9 90.4 | 2.3 2.1 1.8 1.9 1.8 1.9 | 87.4 74.5 63.2 56.4 54.8 44.6 | 10.3 23.4 35.1 41.7 43.4 53.5 | 0.0 0.0 0.0 0.0 0.0 0.0 | 29.8 43.2 47.0 46.7 48.2 40.3 | 3.5 13.6 26.1 34.6 38.2 48.5 |
Comparative example 37-41 and 47-52 are as can be known, with respect to 3-(2-pyridine radicals) pyrazoles silicon-based hybrid material P, the silicon-based hybrid material C of 3-(2-pyridine radicals) pyrazoles and chloropropyl silane graft slightly descends to the activity of dimethyl oxalate and phenol ester exchange reaction, but material C has the overall selectivity of higher MPO and DPO, be that side reaction product reduces, extend at 12 o'clock in the reaction time (seeing embodiment 52), the conversion ratio of DMO and all close with material P to the selectivity of end product DPO, the yield of phenostal reaches 48.5%.
[embodiment 53-65]
With 0.1371 mM nitrogenous organic base is homogeneous catalyst, and the reaction time be 10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 53-65, investigate reaction result.
Table 13: organic acids and base catalysis dimethyl oxalate and phenol ester exchange reaction result
| Embodiment | Catalyst | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 53 54 55 56 57 58 59 60 61 62 63 64 65 | Benzylamine paranitroanilinum parachloroanilinum P-nethoxyaniline aniline methylphenylamine N, accelerine quinoline adenine 2-acetylpyridine pyridine 2,2 '-bipyridyl cyclohexylamine | 84.3 26.1 64.6 73.3 91.8 90.3 94.0 73.3 78.4 72.2 92.6 53.5 69.1 | 28.0 4.0 21.9 24.9 28.6 42.7 51.7 21.3 40.0 9.7 26.7 44.1 35.0 | 47.5 82.4 57.9 54.6 34.1 28.3 21.6 62.2 44.8 63.6 36.8 51.4 52.5 | 24.6 13.6 20.2 20.5 37.2 29.1 26.7 16.6 14.6 26.6 36.4 4.3 12.5 | 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.6 0.0 0.0 0.0 0.0 | 40.0 21.5 37.4 40.0 31.3 25.5 20.3 45.6 35.1 45.9 34.1 27.6 36.3 | ?20.7?3.6?13.0?15.0?34.2?26.2?25.1?12.2?11.4?19.2?33.7?2.3?8.6 |
By embodiment 53-65 as can be known, the existence of nitrogenous organic base has improved the reaction rate of phenol and dimethyl oxalate, and in above-mentioned several nitrogenous organic bases, aniline and pyridine catalyst have demonstrated catalytic activity preferably and to the selectivity of end product DPO.
[embodiment 66-70]
Silicon-based hybrid material with 0.3 gram aniline and chloropropyl silane graft is a heterogeneous catalyst, and the reaction time carried out respectively 2,4,6,8,10 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 66-70, investigate reaction result.
Table 14: the silicon-based hybrid material catalyzed transesterification result of aniline and chloropropyl silane graft
| Embodiment | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | ?AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 66 67 68 69 70 | 2 4 6 8 10 | 68.1 83.2 90.8 96.1 97.3 | 6.4 12.9 12.8 12.6 11.8 | 69.2 56.9 46.3 32.3 28.2 | 24.1 30.2 40.5 54.2 58.7 | 0.4 0.0 0.5 0.8 1.4 | 47.1 47.3 42.0 31.1 27.4 | ?16.4?25.1?36.7?52.1?57.1 |
Comparative example 57 and 70 not only helps reaction mass and catalyst separation after aniline is immobilized as can be known, and catalyst improves the overall selectivity of principal product MPO and DPO.Among the embodiment 70, reaction 10 hours, the yield of phenostal reached 57.1%.
[embodiment 71-75]
With 1.7 mM nitrogenous organic bases is homogeneous catalyst, and the reaction time be 2 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 71-75, investigate reaction result.
Table 15: organic base catalytic dimethyl oxalate and phenol ester exchange reaction result
| Embodiment | Catalyst | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | DPO | ||
| 71 72 73 74 75 | Pyridine aniline octadecylamine Ph 3The P cyclohexylamine | 86.4 76.7 12.8 90.5 89.1 | 88.7 23.2 5.6 88.0 82.5 | 9.3 52.8 91.2 12.0 15.3 | 0.4 19.3 3.3 0 1.3 | 1.7 4.7 0.0 0 0.9 | 8.0 40.5 11.6 10.9 13.5 | 0.3 14.8 0.4 0 1.1 |
By embodiment 71-75 as can be known, aniline has the active and DPO selectivity of higher phenol and dimethyl oxalate ester exchange reaction with respect to above-mentioned several organic acids and base catalyst.When using organic alkali catalyst, this reacts and also can be used for producing methyl phenyl ethers anisole.
[embodiment 76]
With 1.7 mM amino acid is homogeneous catalyst, and the reaction time be 2 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 76, investigate reaction result.
Table 16: amino acid catalytic dimethyl oxalate and phenol ester exchange reaction result
| Embodiment | Catalyst | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | ?AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 76 | The L-proline | 29.0 | ?7.4 | ?85.7 | ?5.4 | 1.5 | 24.8 | ?1.6 |
By embodiment 76 as can be known, the L-proline has higher phenol and dimethyl oxalate ester exchange reaction activity and DPO selectivity.
[embodiment 77]
Mesoporous silicon with 0.3 gram propane sulfonic acid functionalization is catalyst, and the reaction time be 2 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 77, the investigation reaction result.
Table 17: organic acid catalysis dimethyl oxalate and phenol ester exchange reaction result
| Embodiment | Catalyst | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | ?AN | ?MPO | ?DPO | Other | MPO | DPO | ||
| 77 | The mesoporous silicon of propane sulfonic acid functionalization | 70.0 | ?8.4 | ?68.7 | ?18.8 | 0.0 | 48.0 | 13.1 |
By embodiment 77 as can be known, the mesoporous silicon of propane sulfonic acid functionalization is catalyst when carrying out phenol and dimethyl oxalate ester exchange reaction, and reactivity and DPO selectivity are all higher.
[embodiment 78]
In the above-described embodiment, the phenostal of generation all can make diphenyl carbonate through the decarbonylation base.
[Comparative Examples 1-5]
Adopt AlCl respectively
3, Zn (Ac)
2, Ti (OC
4H
9)
4, SnOBu
2Make the ester exchange catalyst of phenol and dimethyl oxalate with dibutyl tin laurate, catalyst consumption is 1.7 mMs, and the reaction time be 2 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form Comparative Examples 1-5, investigate reaction result.
Table 18: the dimethyl oxalate of Comparative Examples and phenol ester exchange reaction result
| Comparative Examples | Catalyst | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | ?MPO | ?DPO | Other | MPO | ?DPO | ||
| 1 | The concentrated sulfuric acid | 68.3 | 12.1 | ?75.3 | 10.4 | 0.0 | 51.4 | 7.1 |
| 2 3 4 5 6 | AlCl 3Zn(Ac) 2Ti(OC 4H 9) 4SnOBu 2Dibutyl tin laurate | 79.8 28.1 92.5 25.7 54.1 | 60.4 35.8 0.0 2.2 1.8 | ?30.8?53.9?20.6?80.8?21.0 | 2.1 2.6 2.8 12.5 13.7 | 6.7 7.7 76.6 4.5 63.5 | 24.6 16.4 19.0 20.8 11.4 | 1.7 0.1 2.6 3.2 7.4 |
Comparing embodiment 77 and Comparative Examples 1 as can be known, the mesoporous silicon of propane sulfonic acid functionalization has the reactivity and the product selectivity of higher dimethyl oxalate and phenol ester exchange reaction than the concentrated sulfuric acid.
Adopt the organic zinc, organic titanium and the organo-tin compound that are widely used as ester exchange catalyst to make catalyst dimethyl oxalate and phenol ester exchange reaction among the Comparative Examples 2-6, these catalyst all contain metal ion, be difficult for separating with reaction system, and catalyst or reactivity are not high, perhaps low to the purpose product selectivity, cause the purpose product yield low.
From embodiment and Comparative Examples 2-6 as can be seen, be in the technology of feedstock production diphenyl carbonate with phenostal and phenol, key technology wherein, be in the step of dimethyl oxalate and phenol ester exchange preparation methyl phenyl oxalate and phenostal, adopt an amount of nitrogenous organic base homogeneous catalyst, especially 3-(2-pyridine radicals) pyrazoles, the purpose product selectivity exceeds the selectivity in the Comparative Examples far away, its reactivity is also high, thereby obtain higher purpose product yield, and stable than homogeneous catalyst in the Comparative Examples, easily separate with reaction mass.
[Comparative Examples 7-11]
The quality percentage composition that adopts reported method among the patent CN200410019331.6 to prepare titanium atom is 10% the catalyst 10wt%TiO of titanium dichloride load on silica gel
2/ SiO
2, with 10wt%TiO
2/ SiO
2Make the catalyst for ester exchange reaction of phenol and dimethyl oxalate, catalyst consumption be 0.3 the gram, and the reaction time carried out respectively 2,4,6,8,10,12 hours, under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form Comparative Examples 6-10, investigate reaction result.
Table 19:10wt%TiO
2/ SiO
2The catalyzed transesterification result
| Comparative Examples | Reaction time (hour) | Conversion ratio (%) | Selectivity (%) | Yield (%) | ||||
| DMO | AN | MPO | DPO | Other | MPO | DPO | ||
| 7 8 9 10 11 | 2 4 6 8 10 | 61.6 69.0 67.8 74.6 74.4 | 0.6 0.7 0.9 0.6 0.8 | 77.3 73.1 71.3 71.9 69.3 | 22.1 26.2 27.8 27.5 29.5 | 0.0 0.0 0.0 0.0 0.4 | 47.6 50.4 48.4 53.6 51.6 | 13.6 18.1 18.9 20.5 21.9 |
10wt%TiO among the Comparative Examples 7-11
2/ SiO
2Catalyst has overall selectivity and the high reaction activity and high of good MPO and DPO, still, and 10wt%TiO
2/ SiO
2Catalyst is lower to the selectivity of end product DPO, and at 10 hours (seeing Comparative Examples 11) of reaction, the yield of phenostal has only 21.9%.
From embodiment and Comparative Examples 7-11 as can be seen, be in the technology of feedstock production diphenyl carbonate with phenostal and phenol, key technology wherein, be in the step of dimethyl oxalate and phenol ester exchange preparation methyl phenyl oxalate and phenostal, adopt supported nitrogenous organic base catalyst, especially 3-(2-pyridine radicals) pyrazoles silicon-based hybrid catalyst and aniline silicon-based hybrid catalyst, the selectivity of purpose product D PO exceeds the selectivity in the Comparative Examples far away, its reactivity is also higher, thereby obtains higher purpose product D PO yield.
In sum, the catalyst that with the organic acids and base is feature is by dimethyl oxalate and phenol ester exchange reaction, synthetic oxalic acid benzene methyl and the phenostal that is used to prepare diphenyl carbonate, for by being raw material with dimethyl oxalate and phenol, elder generation's synthesis of methyl phenyl oxalate, generate phenostal by further ester exchange or disproportionation then, prepare diphenyl carbonate by de-carbonyl reaction again, more strong key core technology is provided.
The invention is not restricted to above embodiment, can make various changes and distortion, only otherwise break away from spirit of the present invention, all should belong to scope of the present invention according to the present invention.
Claims (2)
1. a seed amino acid is characterized in that as the purposes of the catalyst of ester exchange synthesizing aryl ester carboxylic acid described amino acid is the L-proline; Described ester exchange synthesizing aryl ester carboxylic acid is to be starting ester exchange process synthesis of oxalic acid benzene methyl and phenostal with phenol and dimethyl oxalate.
2. according to the purposes of the described amino acid of claim 1 as the catalyst of ester exchange synthesizing aryl ester carboxylic acid, it is characterized in that, in the reactor of rectifying column is housed, with dimethyl oxalate and phenol is raw material, the raw materials components mole ratio dimethyl oxalate: phenol=20: 1～400, and the reaction time is 1～20 hour, reaction temperature is 160～240 ℃, the spontaneous reaction pressure of reactor is 0～1.0MPa, under homogeneous phase L-proline catalyst action, generates phenostal and oxalic acid benzene methyl; The mol ratio of L-proline catalyst and total feed is 1/10000～1/10.
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| CN102600896A (en) * | 2012-01-20 | 2012-07-25 | 山东华阳油业有限公司 | Solid catalyst of bonded type organic sulfonic acid and its preparation method |
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