CN115260033A - Method for preparing diphenyl carbonate and obtained diphenyl carbonate - Google Patents
Method for preparing diphenyl carbonate and obtained diphenyl carbonate Download PDFInfo
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- CN115260033A CN115260033A CN202110479915.5A CN202110479915A CN115260033A CN 115260033 A CN115260033 A CN 115260033A CN 202110479915 A CN202110479915 A CN 202110479915A CN 115260033 A CN115260033 A CN 115260033A
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- 238000000034 method Methods 0.000 title claims abstract description 47
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 51
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 51
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 57
- 239000000376 reactant Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000005686 dimethyl carbonates Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing diphenyl carbonate, which is carried out in a device comprising a reactor and a condenser, and comprises the following steps: filling a molecular sieve between a reactor and a condenser; (2) adding phenol and a catalyst into a reactor; (3) After the temperature is raised, dimethyl carbonate is dripped into the reactor, and diphenyl carbonate is obtained through reaction. The present invention can separate methanol effectively without consuming dimethyl carbonate by using molecular sieve, so that the balance is shifted to the right, and the reactant conversion rate and the product yield are increased.
Description
Technical Field
The invention belongs to the field of preparation of diphenyl carbonate, and particularly relates to a method for preparing diphenyl carbonate and the obtained diphenyl carbonate.
Background
Diphenyl carbonate is an important environmental-friendly chemical product, and is widely applied to the aspects of industry, agriculture, medicine and the like due to the low toxicity and no pollution. There are three main methods for synthesizing diphenyl carbonate: oxidative carbonylation, phosgene, and transesterification. Compared with the former two methods, the ester exchange method has the advantages of relatively mild reaction conditions, small corrosion to equipment, cheap and easily available raw materials, and is a method which is researched more at present. The synthesis of diphenyl carbonate by the transesterification method of dimethyl carbonate and phenol is the most studied method in the transesterification method, and is the only transesterification method for realizing industrialization.
The diphenyl carbonate synthesized by the ester exchange method of dimethyl carbonate and phenol is a reversible reaction, and the reaction principle is as follows:
literature [ Mei Fuming, li guangxing, the theromophilic properties and the xenogenic catalysts for the synthesis of dimethyl carbonates with phenol [ J].Chin.J.Synthetic Chem.，2003，11(4)：320-326.]The thermodynamic properties of the reaction were studied, and at 453K, the equilibrium constant of reaction (1) was 4.0 x 10-3While the equilibrium of reaction (5) is alwaysThe number increases with increasing temperature, so that from a thermodynamic point of view, the reaction of dimethyl carbonate with phenol to diphenyl carbonate is disadvantageous. To increase the yield of diphenyl carbonate, it is necessary to find a more selective catalyst, reduce the formation of by-products, or modify the reaction process to remove the methanol formed and shift the equilibrium to the right.
Since methanol and dimethyl carbonate form 7:3, patent US4252737 discloses a method for increasing the yield of diphenyl carbonate by distilling off the azeotrope to remove methanol, but this method requires the addition of an excess of dimethyl carbonate and is also very difficult to separate the methanol and dimethyl carbonate in the azeotrope. Patent CN104086421A discloses a process for synthesizing diphenyl carbonate by continuous reaction in a fixed bed coupled two-stage rectification tower device, which achieves the purpose of continuous reaction, but methanol still needs to form an azeotrope with dimethyl carbonate to be removed, and in addition, the equipment cost is high, the process is complex, and the investment is large.
Disclosure of Invention
In order to overcome the problems of the prior art, the present invention provides a method for preparing diphenyl carbonate and the obtained diphenyl carbonate, wherein the generated methanol can be removed in time without consuming dimethyl carbonate by using a molecular sieve, thereby improving the conversion rate of reactants and the yield of diphenyl carbonate.
In one aspect, the present invention provides a method for preparing diphenyl carbonate, which is embodied in the following aspects:
1. a method for preparing diphenyl carbonate, said method being carried out in an apparatus comprising a reactor and a condenser, comprising the steps of:
(1) Filling a molecular sieve between the reactor and the condenser;
(2) Adding phenol and a catalyst into a reactor;
(3) After the temperature is raised, dimethyl carbonate is dripped into the reactor, and diphenyl carbonate is obtained through reaction.
2. The process according to 1, wherein the catalyst is selected from the group consisting of organotitanium catalysts and organotin catalysts, preferably from tetraphenyl titanate and/or tetrabutyl titanate.
3. The process according to 1, wherein the molar ratio of the catalyst to the phenol is (0.001 to 0.1): 1, preferably (0.005 to 0.05): 1.
4. The process according to 1, wherein the molar ratio of dimethyl carbonate to phenol is (0.2 to 3): 1, preferably (0.5 to 2): 1.
5. The process according to 1, wherein the temperature is raised to 160 to 260 ℃ in the step (3), preferably to 180 to 220 ℃.
6. The method of claim 1, wherein the molecular sieve has pores greater than 0.38nm and less than 0.47nm, and is preferably selected from a 4A molecular sieve.
7. The method according to 1, wherein the amount of the molecular sieve is 0.2 to 3 times, preferably 0.5 to 2 times the amount of phenol.
8. The method of 1, wherein the molecular sieve is calcined, and preferably, the calcination is performed at 300-800 ℃ for 1-6 h.
9. The method according to any one of the above 1 to 8, wherein the molecular sieve is taken out after the completion of the reaction and subjected to calcination treatment, preferably at 300 to 800 ℃ for 1 to 6 hours.
In another aspect, the present invention provides diphenyl carbonate obtainable by the process according to the first aspect of the present invention.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
It is an object of the present invention to provide a method for preparing diphenyl carbonate, said method being carried out in an apparatus comprising a reactor and a condenser, comprising the steps of:
(1) Filling a molecular sieve between the reactor and the condenser;
(2) Adding phenol and a catalyst into a reactor;
(3) After the temperature is raised, dimethyl carbonate is dripped into the reactor, and diphenyl carbonate is obtained through reaction.
Wherein, the reactor can be a multi-mouth flask or a reaction kettle, and the condenser can be a condenser pipe and the like.
In a preferred embodiment, the catalyst is selected from an organotitanium catalyst and/or an organotin catalyst.
In a further preferred embodiment, the catalyst is selected from at least one of tetraphenyl titanate and/or tetrabutyl titanate.
In a further preferred embodiment, the molar ratio of the catalyst to phenol is (0.001 to 0.1): 1, preferably (0.005 to 0.05): 1.
For example, the molar ratio of the catalyst to phenol is 0.001, 0.002.
In a preferred embodiment, the molar ratio of dimethyl carbonate to phenol is (0.2 to 3): 1, preferably (0.5 to 2): 1.
For example, the molar ratio of dimethyl carbonate to phenol is from 0.2.
In a preferred embodiment, the temperature is raised in step (3) to 160 to 260 ℃, preferably to 180 to 220 ℃.
For example, in step (3), the temperature is raised to 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃.
In this case, the generated methanol and dimethyl carbonate are azeotroped at the increased temperature to form a gas, which moves toward the condenser.
In a preferred embodiment, the pores of the molecular sieve are greater than 0.38nm and less than 0.47nm.
The molecular sieve is a kind of synthetic hydrated aluminosilicate or natural zeolite with the function of screening molecules, and it has many pore channels with uniform pore size and regularly arranged holes in its structure, and the molecular sieves with different pore sizes can separate the molecules with different sizes and shapes. The molecular sieve has the characteristics of high adsorption capacity, strong selectivity, high temperature resistance and the like, and is widely used in organic chemical industry and petrochemical industry.
In a further preferred embodiment, the molecular sieve is selected from 4A molecular sieves.
Wherein the kinetic diameters of the dimethyl carbonate and the methanol are 0.47-0.63 nm and 0.38nm respectively, and the holes of the 4A molecular sieve are 0.4nm, so that the dimethyl carbonate can be just adsorbed and removed. In addition, the molecular sieve can separate out the adsorbed methanol through calcination, and the calcined molecular sieve can be recycled. At present, no report about the application of the molecular sieve to the preparation of diphenyl carbonate exists.
In the invention, the molecular sieve is arranged between the reactor and the condenser, when methanol and dimethyl carbonate azeotrope pass through the molecular sieve, the methanol enters holes of the molecular sieve, and the dimethyl carbonate is condensed and enters the flask to continuously participate in the reaction, thereby improving the conversion rate of reactants. In addition, excessive dimethyl carbonate does not need to be added, and the problem that methanol and dimethyl carbonate in an azeotrope are difficult to separate does not exist.
If the molecular sieve is arranged in the reactor, the effect of separating the methanol from the reaction liquid can not be achieved, only if the molecular sieve is arranged between the reactor and a condenser, the methanol in the azeotrope of the distilled methanol and the dimethyl carbonate can be absorbed, and the dimethyl carbonate flows back to the reactor to continuously participate in the reaction, thereby improving the conversion rate of the phenol.
In a preferred embodiment, the molecular sieve is used in an amount of 0.2 to 3 times, preferably 0.5 to 2 times, the weight of phenol.
In a preferred embodiment, the molecular sieve is calcined.
In a further preferred embodiment, the calcination is carried out at 300 to 800 ℃ for 1 to 6 hours, more preferably at 400 to 600 ℃ for 2 to 5 hours.
In a preferred embodiment, the molecular sieve is removed after the reaction is completed and subjected to a calcination treatment for recycling.
In a further preferred embodiment, the calcination treatment is carried out at 300 to 800 ℃ for 1 to 6 hours, more preferably at 400 to 600 ℃ for 2 to 5 hours.
For example, the calcination temperature is 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃; the calcining time is 1h, 2h, 3h, 4h, 5h and 6h.
It is a second object of the present invention to provide diphenyl carbonate obtained by the process according to the first object of the present invention.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method has low requirement on equipment, simple process and low input cost;
(2) The invention can effectively separate out the methanol without consuming dimethyl carbonate by using the molecular sieve, thereby moving the balance to the right, improving the conversion rate of reactants and the yield of products, and particularly, improving the conversion rate of phenol to 42.02 percent from 3.89 percent after the molecular sieve is added;
(3) The invention does not generate the azeotrope of the dimethyl carbonate and the methanol, does not need to separate the dimethyl carbonate and the methanol, saves energy and reduces cost;
(4) The used molecular sieve can be reused after being recovered and calcined, and the method accords with the current concept of green chemistry.
[ examples ] A method for producing a compound
The invention is further described below by means of specific examples. However, these examples are only illustrative and do not limit the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The 4A molecular sieve adopted in the examples and the comparative examples is from the institute of optothermal fine chemical engineering, tianjin, phenol from Beijing Yili fine chemicals, inc., and dimethyl carbonate from Shanghai reagent, inc.;
the 4A molecular sieve adopted in the embodiment is a calcined 4A molecular sieve, and the calcination conditions are as follows: at 450 ℃ for 5h.
Tetrabutyl titanate can be purchased directly or prepared by referring to patent CN 102675115A.
[ example 1 ]
A100 mL reaction vessel equipped with a stirrer, a heater and a condenser was prepared, and under nitrogen protection, 5g of a 4A molecular sieve was charged between the reaction vessel and the condenser, and 9.4g of phenol and 0.31g of tetraphenyl titanate were added to the reaction vessel. After the heating temperature is raised to 180 ℃, 9g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 42.02%, the selectivity to methylphenyl carbonate was 42.66%, and the selectivity to diphenyl carbonate was 57.24%.
Calcining the reacted molecular sieve: the reaction is carried out for 5h at 450 ℃, and the catalyst is used again after being calcined.
[ example 2 ]
A100 mL reaction vessel equipped with a stirrer, a heater and a condenser was prepared, and under nitrogen protection, a 20g 4A molecular sieve was placed between the reaction vessel and the condenser, and 18.8g of phenol and 0.84g of tetraphenyl titanate were charged into the reaction vessel. After the heating temperature is raised to 180 ℃, 9g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 42.77%, the selectivity to methylphenyl carbonate was 27.94%, and the selectivity to diphenyl carbonate was 72.06%.
Calcining the reacted molecular sieve: the reaction is carried out for 5h at 450 ℃, and the catalyst is used again after being calcined.
[ example 3 ] A method for producing a polycarbonate
A100 mL reaction vessel equipped with a stirrer, a heater and a condenser was prepared, 15g of a 4A molecular sieve was charged between the reaction vessel and the condenser under nitrogen protection, and 18.8g of phenol and 0.84g of tetraphenyl titanate were added to the reaction vessel. After the heating temperature is raised to 180 ℃, 9g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 13.90%, the selectivity to methylphenyl carbonate was 14.31% and the selectivity to diphenyl carbonate was 85.69%.
Calcining the reacted molecular sieve: the reaction is carried out for 5h at 450 ℃, and the catalyst is used again after being calcined.
[ example 4 ] A method for producing a polycarbonate
A100 mL reaction kettle equipped with a stirrer, a heater and a condenser tube was prepared, a 5g 4A molecular sieve was filled between the reaction kettle and the condenser tube under the protection of nitrogen, and 9.4g phenol and 0.42g tetraphenyl titanate were added to the reaction kettle. After the heating temperature is raised to 180 ℃, 18g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 44.60%, the selectivity to methylphenyl carbonate was 40.06%, and the selectivity to diphenyl carbonate was 59.86%.
Calcining the reacted molecular sieve: the reaction is carried out for 5h at 450 ℃, and the catalyst is used again after being calcined.
[ example 5 ] A method for producing a polycarbonate
A100 mL reaction vessel equipped with a stirrer, a heater and a condenser was prepared, and under nitrogen protection, 5g of a 4A molecular sieve was charged between the reaction vessel and the condenser, and 9.4g of phenol and 0.64g of tetraphenyl titanate were added to the reaction vessel. After the heating temperature is raised to 180 ℃, 27g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 46.06%, the selectivity to methylphenyl carbonate was 40.91%, and the selectivity to diphenyl carbonate was 59.03%.
Calcining the reacted molecular sieve: the reaction is carried out for 5h at 450 ℃, and the catalyst is reused after being calcined.
[ COMPARATIVE EXAMPLES ]
Comparative example 1
A100 mL reaction vessel equipped with a stirrer, a heater and a condenser was prepared, and 9.4g of phenol and 0.31g of tetraphenyl titanate were charged into the reaction vessel under a nitrogen atmosphere. After the heating temperature is raised to 180 ℃, 9g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 3.89%, the selectivity to methylphenyl carbonate was 98.15%, and the selectivity to diphenyl carbonate was 1.45%.
Comparative example 2
A100 mL reaction kettle equipped with a stirrer, a heater and a condenser tube was prepared, and under nitrogen protection, 5g of a 3A molecular sieve (cavity less than 0.38 nm) was charged between the reaction kettle and the condenser tube, and 9.4g of phenol and 0.31g of tetraphenyl titanate were added to the reaction kettle. After the heating temperature is raised to 180 ℃, 9g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 5.74%, the selectivity to methylphenyl carbonate was 90.34%, and the selectivity to diphenyl carbonate was 9.54%.
In this comparative example 2, the selectivity to diphenyl carbonate is significantly lower than in example 1.
Comparative example 3
A100 mL reaction vessel equipped with a stirrer, a heater and a condenser was prepared, and under nitrogen protection, 5g of 10X molecular sieve (cavity: more than 0.63 nm) was charged between the reaction vessel and the condenser, and 9.4g of phenol and 0.31g of tetraphenyl titanate were charged into the reaction vessel. After the heating temperature is raised to 180 ℃, 9g of dimethyl carbonate is added dropwise for 3h, and the reaction is continued for 7h after the dropwise addition is finished. The conversion of phenol was 2.68%, the selectivity to methyl phenyl carbonate was 89.25%, and the selectivity to diphenyl carbonate was 9.84%.
In this comparative example 3, the selectivity to diphenyl carbonate is significantly lower than that of example 1.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for preparing diphenyl carbonate, said method being carried out in an apparatus comprising a reactor and a condenser, comprising the steps of:
(1) Filling a molecular sieve between the reactor and the condenser;
(2) Adding phenol and a catalyst into a reactor;
(3) After the temperature is raised, dimethyl carbonate is dripped into the reactor, and diphenyl carbonate is obtained through reaction.
2. The process according to claim 1, characterized in that the catalyst is selected from organotitanium catalysts and/or organotin catalysts, preferably from tetraphenyl titanate and/or tetrabutyl titanate.
3. The process according to claim 1, wherein the molar ratio of catalyst to phenol is (0.001-0.1): 1, preferably (0.005-0.05): 1.
4. The process according to claim 1, wherein the molar ratio of dimethyl carbonate to phenol is (0.2-3): 1, preferably (0.5-2): 1.
5. The process according to claim 1, characterized in that in step (3) the temperature is raised to 160-260 ℃, preferably to 180-220 ℃.
6. The method of claim 1, wherein the molecular sieve has pores larger than 0.38nm and smaller than 0.47nm, preferably selected from 4A molecular sieves.
7. The process according to claim 1, wherein the molecular sieve is used in an amount of 0.2 to 3 times, preferably 0.5 to 2 times, the weight of the phenol.
8. The method according to claim 1, wherein the molecular sieve is calcined, preferably the calcination is carried out at 300-800 ℃ for 1-6 h.
9. The process according to any one of claims 1 to 8, wherein the molecular sieve is removed after the end of the reaction and subjected to a calcination treatment, preferably at a temperature of 300 to 800 ℃ for 1 to 6 hours.
10. Diphenyl carbonate obtainable by the process according to any one of claims 1 to 9.
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