CN114931975A - Catalyst for synthesizing diphenyl carbonate, preparation method and application of diphenyl carbonate - Google Patents
Catalyst for synthesizing diphenyl carbonate, preparation method and application of diphenyl carbonate Download PDFInfo
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- CN114931975A CN114931975A CN202210385168.3A CN202210385168A CN114931975A CN 114931975 A CN114931975 A CN 114931975A CN 202210385168 A CN202210385168 A CN 202210385168A CN 114931975 A CN114931975 A CN 114931975A
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- 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 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 9
- 150000007517 lewis acids Chemical group 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 6
- 230000002195 synergetic effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 53
- 239000007789 gas Substances 0.000 description 15
- 238000011010 flushing procedure Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000010606 normalization Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 organic carbonate compound Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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Abstract
The invention relates to the technical field of organic catalytic synthesis, in particular to a catalyst for synthesizing diphenyl carbonate, a preparation method and application of the diphenyl carbonate, wherein the catalyst is a synergistic catalytic system consisting of a main catalyst and an auxiliary catalyst, the main catalyst is selected from Lewis acid of metal salt, the auxiliary catalyst is selected from trifluoromethanesulfonate, and the amount ratio of the auxiliary catalyst to the main catalyst is 1: 10-50. The invention aims to provide a catalyst for synthesizing diphenyl carbonate, which can directly synthesize the diphenyl carbonate by one-step conversion of carbon dioxide and phenol under the conditions of low pressure and even normal pressure under the catalytic action of the catalyst.
Description
Technical Field
The invention belongs to the technical field of organic catalytic synthesis, and particularly relates to a catalyst for synthesizing diphenyl carbonate, a preparation method and application of the diphenyl carbonate.
Background
Diphenyl carbonate (DPC) is an important organic carbonate compound, is famous for its simple structure, high polarity, low viscosity, low toxicity and easy degradation, has wide application in the fields of electrolyte, organic synthesis, pharmacy, engineering plastics and the like, and is considered as a green chemical intermediate. At present, the DPC synthesis method mainly comprises a phosgene method, an ester exchange method and an oxidative carbonylation method. The traditional synthesis mainly uses phosgene method, needs highly toxic phosgene as raw material, seriously pollutes environment and is gradually eliminated; the ester exchange method adopts dimethyl carbonate, dimethyl oxalate and the like to synthesize DPC with phenol through ester exchange, is influenced by chemical balance, needs a multi-step synthesis process and an additional separation process, has a complex catalytic system, and greatly increases the production cost; the oxidative carbonylation method generally uses a Pd catalyst containing a noble metal, is liable to cause side reactions and difficult to recycle, and uses toxic carbon monoxide gas, which is not favorable for industrial production.
In recent years, the large consumption of global fossil energy has caused a rapid increase in the emission of greenhouse gases, which has caused increasingly severe environmental problems such as global warming and climate abnormality, CO 2 The green and pollution-free C1 resource is one of the main greenhouse gases, and has the advantages of abundant reserves, low price, easy obtainment, safety, no toxicity, renewability and the like. At present, CO is utilized 2 Synthesis of DPC as raw Material CO 2 An important aspect of resource utilization is to make the most abundant CO in the nature 2 The resource is utilized, the use of toxic gases such as phosgene, CO and the like is avoided, no waste is generated, the method is an environment-friendly reaction path, and the method conforms to the current green reaction pathThe concept of color environmental protection is considered to be one of the most promising industrial synthetic routes for synthesizing DPC.
In the prior art, Li Shao-cyclo and the like research on catalysis of CO by Lewis acid 2 The process of directly synthesizing DPC (chem.Lett.,2006,35: 784; J.mol.Catal.A: chem.,2007,264: 255) with phenol, Van national branch and the like researches the catalysis of CO by acid-base auxiliary agent 2 And the influence of direct synthesis of DPC from phenol (Fuel. Process technology, 2011,92: 1052; Aust. J. chem.,2012,65: 1667), but these catalytic systems have the problems of complex catalyst preparation process, high toxicity, high reaction pressure requirement, long reaction time, low yield and selectivity of diphenyl carbonate, and the like, have high requirements on reaction equipment, and are not beneficial to industrial application; patent application No. CN101885682A entitled "a method for directly synthesizing diphenyl carbonate from carbon dioxide and phenol" is also disclosed, but it has the disadvantages of high reaction pressure, poor activity and selectivity, and long reaction time.
In view of the above, the key point of the reaction is to develop a high-efficiency low-cost catalyst, so it is necessary to develop a novel high-efficiency catalyst to improve yield and selectivity of DPC.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing diphenyl carbonate, a preparation method and application of the catalyst, aiming at solving the problems of complex preparation process, high toxicity, high reaction pressure requirement, long reaction time, low yield and selectivity of the diphenyl carbonate and the like in a catalytic system in the prior art.
The invention is realized by the following technical scheme:
the catalyst for synthesizing the diphenyl carbonate is a synergistic catalytic system consisting of a main catalyst and a cocatalyst, the main catalyst is selected from Lewis acid of metal salt, the cocatalyst is selected from trifluoromethanesulfonate, and the amount ratio of the cocatalyst to the main catalyst is 1: 10-50.
Preferably, the ratio of the amount of the cocatalyst to the amount of the main catalyst substance is 1: 30-40.
Preferably, the Lewis acid of the metal salt includes, but is not limited to ZnCl 2 、MgCl 2 、FeCl 3 、Zn(Ac) 2 、Zn(ClO 4 ) 2 。
Preferably, the triflate salt adjuvant includes, but is not limited to, Cu (OTf) 2 、In(OTf) 3 、Ce(OTf) 3 、Bi(OTf) 3 、Yb(OTf) 3 。
Preferably, the Lewis acid of the metal salt is selected from ZnCl 2 Said triflate adjuvant is selected from the group consisting of Cu (OTf) 2 。
The invention also protects the application of the catalyst for synthesizing the diphenyl carbonate in the preparation of the diphenyl carbonate by using the carbon dioxide, and the diphenyl carbonate is prepared by directly converting the carbon dioxide and the phenol as raw materials under low pressure or normal pressure.
The invention also provides a method for catalytically synthesizing diphenyl carbonate by using the catalyst, which comprises the following steps:
phenol and catalyst are mixed in CCl 4 Then introducing CO 2 Reacting the gas at 50-120 ℃ for 0.5-3.0 h to obtain diphenyl carbonate, wherein the solvent is CCl 4 The reaction activity of synthesizing diphenyl carbonate is high.
Preferably, the pressure of the introduced carbon dioxide gas is 0.1-2.0 MPa.
Preferably, the molar ratio of the main catalyst to the phenol is 5-50: 100.
preferably, the yield of the diphenyl carbonate reaches 58.7%, and the selectivity reaches 86.8%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst provided by the invention can be used for catalyzing the synthesis of the diphenyl carbonate under low pressure or even normal pressure, the activity and the selectivity of the synthesis of the diphenyl carbonate are higher, and the yield and the selectivity of the diphenyl carbonate can respectively reach 58.7 percent and 86 percent8%, significantly higher than other catalysts reported in the literature in the prior art. ZnCl 2 /Cu(OTf) 2 Catalytic carbon dioxide Synthesis DPC is a catalytic Process for Lewis acids, Cu (OTf) 2 Can coordinate ZnCl 2 Formation (OTfZnCl) 2 ) H complex, enhanced ZnCl 2 Stability and catalytic ability of (2), and Cu (OTf) 2 Also coordinates phenol, increasing phenol
Acidity, further accelerating the formation of intermediates; furthermore, Cu (OTf) 2 Cu in (1) 2+ Is favorable for quickly activating CO 2 And the reaction efficiency is improved, so that the catalyst has higher yield and selectivity for synthesizing DPC.
(2) The catalyst provided by the invention is insensitive to air and water and has stable performance.
(3) The catalyst provided by the invention has the advantages of small dosage, no toxicity, no harm, short reaction time, safe operation process and contribution to industrial application.
Drawings
FIG. 1 is a schematic diagram of the catalytic synthesis of diphenyl carbonate according to examples 1-9 of the present invention;
FIG. 2 is a hydrogen spectrum of diphenyl carbonate obtained in example 1 of the present invention;
FIG. 3 is a carbon spectrum of diphenyl carbonate produced in example 1 of the present invention;
FIG. 4 is a gas chromatogram of diphenyl carbonate obtained in example 1 of the present invention;
FIG. 5 is a gas chromatogram of diphenyl carbonate obtained in example 2 of the present invention;
FIG. 6 is a gas chromatogram of diphenyl carbonate obtained in example 3 of the present invention;
FIG. 7 is a gas chromatogram of diphenyl carbonate obtained in example 4 of the present invention.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
Example 1
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), ZnCl 2 (3mmol)、Cu(OTf) 2 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 And (3) controlling the pressure in the reaction kettle to be 0.2MPa, heating and stirring the mixture to 100 ℃ for reaction for 2 hours, cooling the mixture to room temperature after the reaction is finished, collecting reaction liquid in the reaction kettle, carrying out centrifugal separation, taking a small amount of liquid, and carrying out quantitative analysis on a product by adopting GC, wherein the yield of the diphenyl carbonate is 58.7 percent, and the selectivity of the diphenyl carbonate is 86.8 percent.
Example 2
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), ZnCl 2 (3mmol)、Cu(OTf) 2 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 And (3) controlling the pressure in the reaction kettle to be 2MPa, heating and stirring the mixture to 100 ℃ for reaction for 2 hours, cooling the mixture to room temperature after the reaction is finished, collecting reaction liquid in the reaction kettle, carrying out centrifugal separation, taking a small amount of liquid, and carrying out quantitative analysis on a product by adopting GC, wherein the yield of the diphenyl carbonate is 63.2%, and the selectivity of the diphenyl carbonate is 81.2%.
Example 3
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), MgCl 2 (3mmol)、Cu(OTf) 2 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL autoclave with high purity CO 2 Displacing air in the apparatus, flushing CO 2 Heating and stirring to 100 deg.C under 0.2MPa for 2 hr, cooling to room temperature, collecting reaction liquid, centrifugingAfter separation, a small amount of liquid was taken to conduct quantitative analysis on the product by GC, the yield of diphenyl carbonate was 54.1%, and the selectivity of diphenyl carbonate was 79.3%.
Example 4
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), MgCl 2 (3mmol)、Yb(OTf) 3 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 The pressure in the reaction kettle is controlled to be 0.2MPa, the reaction kettle is heated and stirred to 100 ℃ for reaction for 1 hour, after the reaction is finished, the reaction kettle is cooled to room temperature, reaction liquid in the reaction kettle is collected and centrifugally separated, a small amount of liquid is taken, products are quantitatively analyzed by GC, the yield of the diphenyl carbonate is 29.5 percent, and the selectivity of the diphenyl carbonate is 75.8 percent.
Example 5
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), MgCl 2 (3mmol)、Yb(OTf) 3 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL autoclave with high purity CO 2 Displacing air in the apparatus, flushing CO 2 The pressure in the reaction kettle is controlled to be 0.2MPa, the reaction kettle is heated and stirred to 100 ℃ for reaction for 2 hours, after the reaction is finished, the reaction solution is cooled to room temperature, the reaction solution in the reaction kettle is collected and centrifugally separated, a small amount of liquid is taken, products are quantitatively analyzed by GC, the yield of the diphenyl carbonate is 52.1 percent, and the selectivity of the diphenyl carbonate is 82.3 percent.
Example 6
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), Zn (Ac) 2 (3mmol)、In(OTf) 3 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL autoclave with high purity CO 2 Displacing air in the apparatus, flushing CO 2 Heating and stirring to 100 deg.C under 0.2MPa for 2 hr, cooling to room temperature, collecting reaction liquid, centrifuging, collecting small amount of liquid, and quantifying by GCThe yield of diphenyl carbonate was 49.5% and the selectivity to diphenyl carbonate was 78.8% by analysis.
Example 7
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), Zn (Ac) 2 (3mmol)、Bi(OTf) 3 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 The pressure in the reaction kettle is controlled to be 0.2MPa, the reaction kettle is heated and stirred to 100 ℃ for reaction for 2 hours, after the reaction is finished, the reaction solution is cooled to room temperature, the reaction solution in the reaction kettle is collected and centrifugally separated, a small amount of liquid is taken, the product is quantitatively analyzed by GC, the yield of the diphenyl carbonate is 52.3 percent, and the selectivity of the diphenyl carbonate is 83.2 percent.
Example 8
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), Zn (ClO) 4 ) 2 (3mmol)、Cu(OTf) 2 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 And (3) controlling the pressure in the reaction kettle to be 0.2MPa, heating and stirring the mixture to 100 ℃ for reaction for 2 hours, cooling the mixture to room temperature after the reaction is finished, collecting reaction liquid in the reaction kettle, carrying out centrifugal separation, taking a small amount of liquid, and carrying out quantitative analysis on a product by adopting GC, wherein the yield of the diphenyl carbonate is 54.2%, and the selectivity of the diphenyl carbonate is 76.7%.
Example 9
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), Zn (ClO) 4 ) 2 (3mmol)、Ce(OTf) 3 (0.125mmol) and CCl 4 (15mmol) was added to a 25mL autoclave with high purity CO 2 Displacing air in the apparatus, flushing CO 2 Heating and stirring to 100 deg.C under 0.2MPa for 2 hr, cooling to room temperature, collecting reaction liquid, centrifuging, collecting small amount of liquid, quantitatively analyzing by GC, and collecting diphenyl carbonateThe yield of the ester was 52.4% and the selectivity to diphenyl carbonate was 77.8%.
Example 10
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (60mmol), ZnCl 2 (3mmol)、Cu(OTf) 2 (0.3mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 And (3) heating and stirring the pressure in the reaction kettle to be 1MPa, heating the mixture to 120 ℃ for reaction for 0.5 hour, cooling the mixture to room temperature after the reaction is finished, collecting reaction liquid in the reaction kettle, and performing centrifugal separation to obtain the diphenyl carbonate.
Example 11
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6mmol), ZnCl 2 (3mmol)、Cu(OTf) 2 (0.06mmol) and CCl 4 (15mmol) was added to a 25mL reactor and high purity CO was used 2 Displacing air in the apparatus, flushing CO 2 Heating and stirring the mixture to 50 ℃ under the pressure of 0.1MPa in the reaction kettle, reacting for 3 hours, cooling the mixture to room temperature after the reaction is finished, collecting reaction liquid in the reaction kettle, and performing centrifugal separation to obtain the diphenyl carbonate.
The results of fig. 2-3 show that diphenyl carbonate can be produced using the catalysts of the present application.
As can be seen from the gas chromatogram of diphenyl carbonate obtained in fig. 4, a small amount of the reaction solution was detected by the modified normalization method on a gas chromatograph of the shanghai tianmei 7980 type, and the results of quantitative analysis showed that the yield and selectivity of diphenyl carbonate were 58.7% and 86.8%.
As can be seen from the gas chromatogram of diphenyl carbonate obtained in fig. 5, a small amount of the reaction solution was detected by the modified normalization method on a gas chromatograph of the shanghai tianmei 7980 type, and the results of quantitative analysis showed that the yield and selectivity of diphenyl carbonate were 63.2% and 81.2%.
As can be seen from the gas chromatogram of diphenyl carbonate obtained in fig. 6, when a small amount of the reaction solution was detected by the modified normalization method on a gas chromatograph of shanghai tianmei 7980 type, a distinct diphenyl carbonate signal peak was observed, and quantitative analysis results showed that the yield and selectivity of diphenyl carbonate were 54.1% and 79.3%.
As can be seen from the gas chromatogram of the diphenyl carbonate obtained in fig. 7, when a small amount of the reaction solution was detected by the modified normalization method on a gas chromatograph of shanghai tianmei 7980 type, a distinct diphenyl carbonate signal peak was observed, and quantitative analysis results showed that the yield and selectivity of diphenyl carbonate were 29.5% and 75.8%.
The results of the above figures show ZnCl 2 /Cu(OTf) 2 The catalyst can catalyze carbon dioxide and phenol to convert at one step under low pressure or even normal pressure to directly synthesize diphenyl carbonate, has higher yield and selectivity for the target product diphenyl carbonate, is obviously higher than other catalysts reported in documents in the prior art, has less dosage, is nontoxic and harmless, and is a novel high-efficiency catalyst.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (10)
1. The catalyst for synthesizing the diphenyl carbonate is characterized in that the catalyst is a synergistic catalytic system consisting of a main catalyst and a cocatalyst, the main catalyst is selected from Lewis acid of metal salt, the cocatalyst is selected from trifluoromethanesulfonate, and the amount ratio of the cocatalyst to the main catalyst is 1: 10-50.
2. The catalyst for synthesizing diphenyl carbonate according to claim 1, wherein the ratio of the amounts of the cocatalyst to the main catalyst material is 1: 30-40.
3. The catalyst for the synthesis of diphenyl carbonate according to claim 1, characterized in that the Lewis acid of the metal salt includes but is not limited to ZnCl 2 、MgCl 2 、FeCl 3 、Zn(Ac) 2 、Zn(ClO 4 ) 2 。
4. The diphenyl carbonate synthesis catalyst according to claim 2, wherein the triflate salt promoter includes but is not limited to Cu (OTf) 2 、In(OTf) 3 、Ce(OTf) 3 、Bi(OTf) 3 、Yb(OTf) 3 。
5. The catalyst for the synthesis of diphenyl carbonate according to claim 3, characterized in that the Lewis acid of the metal salt is selected from ZnCl 2 Said triflate adjuvant is selected from the group consisting of Cu (OTf) 2 。
6. Use of the catalyst for synthesizing diphenyl carbonate according to any one of claims 1 to 5 in the preparation of diphenyl carbonate from carbon dioxide, wherein the diphenyl carbonate is prepared by directly converting carbon dioxide and phenol as raw materials at low pressure or normal pressure.
7. A method for the catalytic synthesis of diphenyl carbonate using the catalyst of claim 1, comprising the steps of:
phenol and catalyst are mixed in CCl 4 Then introducing CO 2 Reacting the gas at 50-120 ℃ for 0.5-3.0 h to obtain the diphenyl carbonate.
8. The method for catalytic synthesis of diphenyl carbonate with the catalyst according to claim 7, wherein the carbon dioxide gas is introduced at a pressure of 0.1 to 2.0 MPa.
9. The method for catalytically synthesizing diphenyl carbonate with the catalyst according to claim 7, wherein the molar ratio of the main catalyst to phenol is 5 to 50: 100.
10. the method for catalytic synthesis of diphenyl carbonate with the catalyst according to claim 7, wherein the yield of diphenyl carbonate is 58.7% and the selectivity is 86.8%.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3005684B1 (en) * | 1999-03-10 | 2000-01-31 | 工業技術院長 | Method for producing carbonate ester |
| CN1775734A (en) * | 2005-12-06 | 2006-05-24 | 河北工业大学 | Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process |
| CN101198580A (en) * | 2005-04-12 | 2008-06-11 | 独立行政法人产业技术综合研究所 | Processes for production of carbonic esters |
| CN101254460A (en) * | 2008-03-26 | 2008-09-03 | 中国科学院成都有机化学有限公司 | Process for preparing multiphase catalysts for ester exchange synthesizing diphenyl carbonate |
| CN101885682A (en) * | 2010-06-25 | 2010-11-17 | 武汉工业学院 | Method for directly synthesizing diphenyl carbonate by carbon dioxide and phenol |
| US20110152558A1 (en) * | 2009-12-21 | 2011-06-23 | China Petrochemical Development Corporation | Process for producing diaryl carbonates |
| CN102531908A (en) * | 2011-12-21 | 2012-07-04 | 陕西省石油化工研究设计院 | Preparation method of methyl phenyl carbonic ester |
| CN108722478A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | The preparation method and its catalyst of dipheryl carbonate esters compound and application |
| CN109265344A (en) * | 2017-07-18 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of dipheryl carbonate esters compound |
| CN109678722A (en) * | 2018-12-25 | 2019-04-26 | 常熟市常吉化工有限公司 | A kind of linear carbonate and its synthetic method containing fluoroalkyl |
| CN111495423A (en) * | 2020-04-22 | 2020-08-07 | 河南科技学院 | Immobilized functionalized ionic liquid catalyst and application thereof in diphenyl carbonate synthesis |
| CN113087740A (en) * | 2021-04-09 | 2021-07-09 | 河南科技学院 | Preparation method and application of organic tin ionic liquid catalyst |
| CN114011459A (en) * | 2021-11-16 | 2022-02-08 | 沈阳工业大学 | Titanium series double-acid type ionic liquid catalyst, preparation method and application |
-
2022
- 2022-04-13 CN CN202210385168.3A patent/CN114931975B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3005684B1 (en) * | 1999-03-10 | 2000-01-31 | 工業技術院長 | Method for producing carbonate ester |
| CN101198580A (en) * | 2005-04-12 | 2008-06-11 | 独立行政法人产业技术综合研究所 | Processes for production of carbonic esters |
| CN1775734A (en) * | 2005-12-06 | 2006-05-24 | 河北工业大学 | Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process |
| CN101254460A (en) * | 2008-03-26 | 2008-09-03 | 中国科学院成都有机化学有限公司 | Process for preparing multiphase catalysts for ester exchange synthesizing diphenyl carbonate |
| US20110152558A1 (en) * | 2009-12-21 | 2011-06-23 | China Petrochemical Development Corporation | Process for producing diaryl carbonates |
| CN101885682A (en) * | 2010-06-25 | 2010-11-17 | 武汉工业学院 | Method for directly synthesizing diphenyl carbonate by carbon dioxide and phenol |
| CN102531908A (en) * | 2011-12-21 | 2012-07-04 | 陕西省石油化工研究设计院 | Preparation method of methyl phenyl carbonic ester |
| CN108722478A (en) * | 2017-04-24 | 2018-11-02 | 中国石油化工股份有限公司 | The preparation method and its catalyst of dipheryl carbonate esters compound and application |
| CN109265344A (en) * | 2017-07-18 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of dipheryl carbonate esters compound |
| CN109678722A (en) * | 2018-12-25 | 2019-04-26 | 常熟市常吉化工有限公司 | A kind of linear carbonate and its synthetic method containing fluoroalkyl |
| CN111495423A (en) * | 2020-04-22 | 2020-08-07 | 河南科技学院 | Immobilized functionalized ionic liquid catalyst and application thereof in diphenyl carbonate synthesis |
| CN113087740A (en) * | 2021-04-09 | 2021-07-09 | 河南科技学院 | Preparation method and application of organic tin ionic liquid catalyst |
| CN114011459A (en) * | 2021-11-16 | 2022-02-08 | 沈阳工业大学 | Titanium series double-acid type ionic liquid catalyst, preparation method and application |
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