CN114931975B - 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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- CN114931975B CN114931975B CN202210385168.3A CN202210385168A CN114931975B CN 114931975 B CN114931975 B CN 114931975B CN 202210385168 A CN202210385168 A CN 202210385168A CN 114931975 B CN114931975 B CN 114931975B
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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 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 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
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 230000002195 synergetic effect Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 82
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- 239000007789 gas Substances 0.000 description 15
- 238000004445 quantitative analysis Methods 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 238000010438 heat treatment Methods 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 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
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 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
- 230000004913 activation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 230000007547 defect Effects 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
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 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
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 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
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 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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- 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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- 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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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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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 of diphenyl carbonate and application thereof, wherein the catalyst is a synergistic catalytic system consisting of a main catalyst and a cocatalyst, the main catalyst is Lewis acid of metal salt, the cocatalyst is trifluoro methanesulfonate, and the mass ratio of the cocatalyst to the main catalyst is 1:10-50. The invention aims to provide a catalyst for synthesizing diphenyl carbonate, which is used for directly synthesizing diphenyl carbonate by one-step conversion of carbon dioxide and phenol under the catalysis of the catalyst and even under the condition of low pressure and normal pressure, and the result shows that the catalyst has higher yield and selectivity on diphenyl carbonate.
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 diphenyl carbonate.
Background
Diphenyl carbonate (DPC) is an important organic carbonate compound, known for its simple structure, high polarity, low viscosity, low toxicity, and easy degradation, and has wide application in the fields of electrolytes, organic synthesis, pharmacy, engineering plastics, etc., and is considered as a green chemical intermediate. At present, the synthesis method of DPC mainly comprises a phosgene method, an ester exchange method and an oxidative carbonylation method. The traditional synthesis mainly uses a phosgene method, and needs to use highly toxic phosgene as a raw material, so that the environment is seriously polluted, and the method is gradually eliminated; the transesterification method adopts dimethyl carbonate, dimethyl oxalate and the like to synthesize DPC with phenol through transesterification, and the method is influenced by chemical balance, and needs a multi-step synthesis process and an additional separation process, so that a catalytic system is complex, and the production cost is greatly increased; the oxidative carbonylation method generally uses a Pd catalyst containing noble metal, is easy to cause side reactions, is difficult to recycle, and uses toxic carbon monoxide gas, thus being unfavorable for industrial production.
In recent years, the global consumption of fossil energy has drastically increased the emission of greenhouse gases, which causes increasingly serious environmental problems such as global warming and climate abnormality, and CO 2 As one of main greenhouse gases, the method is also a green pollution-free C1 resource, and has the advantages of abundant reserves, low cost, easy obtainment, safety, no toxicity, reproducibility and the like. Currently, CO is utilized 2 DPC is synthesized from CO 2 An important aspect of resource utilization is that the most abundant CO in nature 2 The resource is utilized, so that 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, accords with the current environment-friendly concept, and is considered as one of the most promising industrial synthesis routes for synthesizing DPC.
In the prior art, li Zhenhuan et al studied Lewis acid catalyzed CO 2 And a direct synthesis process of DPC (Chem.Lett., 2006,35:784;J.Mol.Catal.A:Chem, 2007, 264:255), fan Guozhi and the like are researched to catalyze CO by using acid-base auxiliary agents 2 And the influence of direct synthesis of DPC by phenol (fuel. Process technology, 2011,92:1052; aust. J. Chem.,2012, 65:1667.), but 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 exist in the catalytic systems, and the requirements on reaction equipment are high, so that the industrial application is not facilitated; patent application with the application number of CN101885682A, named as a method for directly synthesizing diphenyl carbonate from carbon dioxide and phenol, is also disclosed, but has the defects of high reaction pressure, poor activity and selectivity and long reaction time.
In view of the foregoing, the key to this reaction is to develop efficient and low cost catalysts, and therefore, it is necessary to develop novel efficient catalysts to increase DPC yield and selectivity.
Disclosure of Invention
In order to solve the problems of complex preparation process, high toxicity, high reaction pressure requirement, long reaction time, low yield and selectivity of diphenyl carbonate and the like of a catalyst system in the prior art, the invention provides a catalyst for synthesizing diphenyl carbonate, a preparation method and application of the diphenyl carbonate.
The invention is realized by the following technical scheme:
the catalyst for synthesizing diphenyl carbonate is a synergistic catalytic system consisting of a main catalyst and a cocatalyst, wherein the main catalyst is Lewis acid of metal salt, the cocatalyst is triflate, and the mass ratio of the cocatalyst to the main catalyst is 1:10-50.
Preferably, the ratio of the cocatalyst to the procatalyst material is in the range of 1:30 to 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 aid 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 The triflate auxiliary is selected from Cu (OTf) 2 。
The invention also protects the application of the catalyst for synthesizing diphenyl carbonate in preparing diphenyl carbonate by using carbon dioxide, wherein the diphenyl carbonate is prepared by directly converting carbon dioxide and phenol serving as raw materials under low pressure or normal pressure.
The invention also provides a method for synthesizing diphenyl carbonate by catalyzing with the catalyst, which comprises the following steps:
mixing phenol and catalyst in CCl 4 Then CO is introduced into 2 Reacting the gas at 50-120 ℃ for 0.5-3.0 h to obtain diphenyl carbonate, wherein the solvent is CCl after research 4 The reaction activity for synthesizing diphenyl carbonate is high.
Preferably, the pressure of the carbon dioxide gas is 0.1-2.0 MPa.
Preferably, the molar ratio of the main catalyst to 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 catalyze the synthesis of diphenyl carbonate at low pressure even normal pressure, the activity and selectivity of the synthesized diphenyl carbonate are high, and the yield and selectivity of the diphenyl carbonate can reach 58.7% and 86.8% respectively, which are obviously higher than other catalysts reported in the literature in the prior art. ZnCl 2 /Cu(OTf) 2 Catalyzing carbon dioxide synthesis DPC is a catalytic process of Lewis acids, cu (OTf) 2 Can coordinate ZnCl 2 Formation (OTfZnCl) 2 ) H complex, reinforcing ZnCl 2 While Cu (OTf) 2 Also coordinates phenol, increases phenol
The acidity further accelerates the formation of intermediates; furthermore, cu (OTf) 2 Cu in (B) 2+ Is beneficial to the rapid activation of CO 2 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 or harm, short reaction time, safe operation process and contribution to industrial application.
Drawings
FIG. 1 is a diagram showing the mechanism of catalytic synthesis of diphenyl carbonate according to examples 1 to 9 of the present invention;
FIG. 2 is a graph showing the hydrogen spectrum of diphenyl carbonate produced in example 1 of the present invention;
FIG. 3 is a graph showing the carbon spectrum of diphenyl carbonate produced in example 1 of the present invention;
FIG. 4 is a gas chromatogram of diphenyl carbonate produced in example 1 of the present invention;
FIG. 5 is a gas chromatogram of diphenyl carbonate produced in example 2 of the present invention;
FIG. 6 is a gas chromatogram of diphenyl carbonate produced 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, but it should be understood that the invention is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
Example 1
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), znCl 2 (3mmol)、Cu(OTf) 2 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 58.7%, and the selectivity of the diphenyl carbonate is 86.8%.
Example 2
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), znCl 2 (3mmol)、Cu(OTf) 2 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 63.2%, and the selectivity of diphenyl carbonate is 81.2%.
Example 3
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), mgCl 2 (3mmol)、Cu(OTf) 2 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 54.1%, and the selectivity of diphenyl carbonate is 79.3%.
Example 4
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), mgCl 2 (3mmol)、Yb(OTf) 3 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for reaction for 1h, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 29.5%, and the selectivity of diphenyl carbonate is 75.8%.
Example 5
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), mgCl 2 (3mmol)、Yb(OTf) 3 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 52.1%, and the selectivity of diphenyl carbonate is 82.3%.
Example 6
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), zn (Ac) 2 (3mmol)、In(OTf) 3 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 49.5%, and the selectivity of diphenyl carbonate is 78.8%.
Example 7
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), zn (Ac) 2 (3mmol)、Bi(OTf) 3 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 52.3%, and the selectivity of diphenyl carbonate is 83.2%.
Example 8
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), zn (ClO) 4 ) 2 (3mmol)、Cu(OTf) 2 (0.125mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 54.2%, and the selectivity of diphenyl carbonate is 76.7%.
Example 9
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), zn (ClO) 4 ) 2 (3mmol)、Ce(OTf) 3 (0.125 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 The pressure in the reaction kettle is 0.2MPa, the reaction kettle is heated, stirred and warmed to 100 ℃ for 2 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the reaction liquid in the reaction kettle is collected, centrifugal separation is carried out, a small amount of liquid is taken, the quantitative analysis is carried out on the product by adopting GC, the yield of diphenyl carbonate is 52.4%, and the selectivity of diphenyl carbonate is 77.8%.
Example 10
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (60 mmol), znCl 2 (3mmol)、Cu(OTf) 2 (0.3 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 And (3) heating, stirring and heating the pressure in the reaction kettle to 120 ℃ to react for 0.5h, cooling to room temperature after the reaction is finished, collecting reaction liquid in the reaction kettle, and centrifugally separating to obtain diphenyl carbonate.
Example 11
A method for synthesizing diphenyl carbonate comprises the following steps:
phenol (6 mmol), znCl 2 (3mmol)、Cu(OTf) 2 (0.06 mmol) and CCl 4 (15 mmol) was added to a 25mL reaction vessel and treated with high purity CO 2 Air in the device is replaced and is flushed into CO 2 Internal pressure of the reaction kettleAnd heating, stirring and heating to 50 ℃ with the force of 0.1MPa for reaction for 3 hours, cooling to room temperature after the reaction is finished, collecting reaction liquid in a reaction kettle, and centrifugally separating to obtain diphenyl carbonate.
The results in FIGS. 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 reaction solution is detected on a gas chromatograph of Shanghai Tianmei 7980 by adopting a correction normalization method, and the reaction solution has obvious diphenyl carbonate signal peaks, and the quantitative analysis result shows that the yield and the selectivity of the diphenyl carbonate are 58.7% and 86.8%.
As can be seen from the gas chromatogram of diphenyl carbonate prepared in FIG. 5, a small amount of reaction solution is detected on a gas chromatograph of Shanghai Tianmei 7980 by adopting a correction normalization method, and the reaction solution has obvious diphenyl carbonate signal peaks, and the quantitative analysis result shows that the yield and selectivity of the diphenyl carbonate are 63.2% and 81.2%.
As can be seen from the gas chromatogram of diphenyl carbonate obtained in FIG. 6, a small amount of reaction solution is detected on a gas chromatograph of Shanghai Tianmei 7980 by adopting a correction normalization method, and the reaction solution has obvious diphenyl carbonate signal peaks, and the quantitative analysis result shows that the yield and the selectivity of the diphenyl carbonate are 54.1% and 79.3%.
As can be seen from the gas chromatogram of diphenyl carbonate obtained in FIG. 7, a small amount of reaction solution was detected by a correction normalization method on a gas chromatograph of Shanghai Tianmei 7980, and the reaction solution had an obvious diphenyl carbonate signal peak, and the quantitative analysis result showed that the yield and selectivity of diphenyl carbonate were 29.5% and 75.8%.
The results of the above figures show that ZnCl 2 /Cu(OTf) 2 The catalyst can catalyze the one-step conversion of carbon dioxide and phenol to directly synthesize diphenyl carbonate at low pressure even normal pressure, has higher yield and selectivity to the target product diphenyl carbonate, is obviously higher than other catalysts reported in the literature in the prior art, has less catalyst consumption, is nontoxic and harmless, and is a novel high-efficiency catalyst.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.
Claims (6)
1. The catalyst for synthesizing diphenyl carbonate is characterized in that the catalyst is a synergistic catalytic system consisting of a main catalyst and a cocatalyst, wherein the main catalyst is Lewis acid of metal salt, the cocatalyst is trifluoro methanesulfonate, and the ratio of the cocatalyst to the main catalyst is 1:24-40;
the Lewis acid of the metal salt comprises ZnCl 2 、MgCl 2 、FeCl 3 、Zn(Ac) 2 、Zn(ClO 4 ) 2 ；
The triflate salt comprises Cu (OTf) 2 、In(OTf) 3 、Ce(OTf) 3 、Bi(OTf) 3 、Yb(OTf) 3 。
2. The catalyst for synthesizing diphenyl carbonate according to claim 1, wherein the Lewis acid of the metal salt is selected from ZnCl 2 The triflate is selected from Cu (OTf) 2 。
3. The use of the catalyst for synthesizing diphenyl carbonate according to any one of claims 1-2 in preparing diphenyl carbonate by using carbon dioxide, wherein the diphenyl carbonate is prepared by directly converting carbon dioxide and phenol as raw materials under low pressure or normal pressure.
4. Use of a catalyst for synthesizing diphenyl carbonate according to claim 3 in the preparation of diphenyl carbonate from carbon dioxide, comprising the steps of:
mixing phenol and catalyst in CCl 4 Then CO is introduced into 2 And (3) reacting the gas at 50-120 ℃ for 0.5-3.0 h to obtain diphenyl carbonate.
5. The use of the catalyst for synthesizing diphenyl carbonate according to claim 4 in preparing diphenyl carbonate from carbon dioxide, wherein the pressure of introducing carbon dioxide gas is 0.1-2.0 MPa.
6. The use of the catalyst for synthesizing diphenyl carbonate according to claim 4 in preparing diphenyl carbonate from carbon dioxide, wherein the molar ratio of the main catalyst to phenol is 5-50: 100.
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