CN103524341A - Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate - Google Patents

Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate Download PDF

Info

Publication number
CN103524341A
CN103524341A CN201310374161.2A CN201310374161A CN103524341A CN 103524341 A CN103524341 A CN 103524341A CN 201310374161 A CN201310374161 A CN 201310374161A CN 103524341 A CN103524341 A CN 103524341A
Authority
CN
China
Prior art keywords
acid ion
ion liquid
phenol
reaction
oxalate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310374161.2A
Other languages
Chinese (zh)
Other versions
CN103524341B (en
Inventor
罗能镇
相咸高
徐义明
黄益平
计立
钱超
陈新志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
China Construction Industrial and Energy Engineering Group Co Ltd
Original Assignee
Zhejiang University ZJU
China Construction Industrial Equipment Installation Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU, China Construction Industrial Equipment Installation Co Ltd filed Critical Zhejiang University ZJU
Priority to CN201310374161.2A priority Critical patent/CN103524341B/en
Publication of CN103524341A publication Critical patent/CN103524341A/en
Application granted granted Critical
Publication of CN103524341B publication Critical patent/CN103524341B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses an application of a Br phi nsted acid ion liquid to preparation of diphenyl oxalate. Phenol and dimethyl oxalate are subjected to transesterification under the catalytic action of the Br phi nsted acid ion liquid, and the transesterification is carried out under a solvent-free condition, so that a mixture with diphenyl oxalate is obtained, wherein the reaction temperature ranges from 150 DEG C to 250 DEG C, the reaction time ranges from 2h to 5h, the mole ratio of phenol to diphenyl oxalate is (2.0-10.0):1, and the mole ratio of the Br phi nsted acid ion liquid as a catalyst to dimethyl oxalate as a substrate is 5-20%. By using the method, diphenyl oxalate (namely the mixture with diphenyl oxalate is obtained) can be greenly and safely prepared through the transesterification between phenol and dimethyl oxalate under mild reaction conditions and at high yield and low cost.

Description

The application of Br φ nsted acid ion liquid in preparing phenyloxalate
Technical field
The present invention relates to a kind of methodology of organic synthesis, particularly
Figure BDA0000371791280000012
the application of acid ion liquid in preparing phenyloxalate (DPO).
Background technology
Diphenyl carbonate (DPC) is a kind of low toxicity, free of contamination important organic carbonate, can be used for polycarbonate synthesis, methyl p-hydroxybenzoate, monoisocyanates etc., is widely used in plastics industry, synthetic pesticide, medicine and other fields.
Phenyloxalate (DPO) can obtain diphenyl carbonate through de-carbonyl reaction, and this reaction has ripe technique.
The synthetic method of DPC mainly contains three kinds at present:
1) phosgenation is first reacted with phenol by phosgene and generates phenyl chloroformate in NaOH, then synthesizes DPC(S-1 with phenol reactant);
2) ester-interchange method, comprises phenol and methylcarbonate (DMC) ester-interchange method (S-2), phenol and dimethyl oxalate (DMO) ester-interchange method (S-3), and gained phenyloxalate decarbonylation base obtains product D PC;
3) oxidative carbonylation method, with CO, O 2with phenol be raw material direct synthetic DPC(S-4 under catalyst action).
Figure BDA0000371791280000013
Figure BDA0000371791280000021
Wherein, the synthetic DPC of phenol and DMO ester-interchange method is easy to the advantage such as separated because reaction conditions is gentle, atom utilization is high with by product and has wide industrial prospect.The synthetic DPC of phenol and DMO transesterify completes conventionally under condition of normal pressure, and this reaction is, by phenol and DMO, transesterification reaction oxalic diphenyl ester (DPO) first occurs, more isolated DPO is generated to DPC through de-carbonyl reaction.This technique is compared with methylcarbonate (DMC) ester-interchange method with phenol, although generate equally by-product carbinol, but methyl alcohol and DMO do not form azeotrope, by simple rectifying, just separating methanol can be gone out to reaction system, thereby contribute to transesterification reaction forward to carry out, improve DPO yield, by product CO, methyl alcohol can synthesize DMO again by nitrous acid ester gas phase coupling method in addition, realize recycle, reduce production costs.Yield and the selectivity of the de-oxo process DPC of DPO are all very high simultaneously, are conducive to realize suitability for industrialized production.
The defects such as the synthetic DPC of phenol and DMO transesterify react the homogeneous catalysis systems such as organic compound of general employing Lewis acid or titaniferous, tin, and average life is short, difficult separation and recycling, equipment corrosion are serious, are unfavorable for suitability for industrialized production.Although and heterogeneous catalyst can partly overcome many drawbacks of homogeneous catalyst, simplify sepn process, such catalyst preparation process is complicated, is still difficult to reach industrialized requirement at aspects such as stability, activity.
According to bibliographical information, existing heterogeneous catalyst comprises Modified MCM-41 molecular sieve (reference: Liu, Y.; Zhao, G.; Zhu, W.; Wang, J.; Liu, G.; Zhang, W.; Jia, M.Journal Of The Brazilian Chemical Society 2010,21,2254-2261.), MoO 3/ SiO 2(reference: Gong Jinlong. loading type MoO 3the research [D] of catalysis dimethyl oxalate and phenol ester permutoid reaction synthesis of oxalic acid diphenyl ester. University Of Tianjin, 2004.), TiO 2/ SiO 2(reference: Wang Shengping. phenol and dimethyl oxalate synthesis of diphenyl carbonate by ester exchange reaction [D]. University Of Tianjin, 2003.) etc., all there is the problems such as the yield of methylcarbonate transformation efficiency and diphenyl carbonate is lower.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of the application of acid ion liquid in preparing phenyloxalate (DPO), adopt the method energy realization response mild condition, yield is high, cost is low, utilize phenol and dimethyl oxalate transesterify to prepare phenyloxalate (that is the mixture that, acquisition contains phenyloxalate) green safety.
In order to solve the problems of the technologies described above, the invention provides a kind of
Figure BDA0000371791280000023
the application of acid ion liquid in preparing phenyloxalate (DPO), phenol and dimethyl oxalate (DMO) exist
Figure BDA0000371791280000024
under the katalysis of acid ion liquid, carry out transesterification reaction, transesterification reaction is carried out under condition of no solvent, and temperature of reaction is 150～250 ℃, and the reaction times is 2～5h, must contain the mixture of phenyloxalate (DPO);
The mol ratio of phenol and dimethyl oxalate (DMO) is 2.0～10.0:1;
As catalyzer
Figure BDA0000371791280000031
acid ion liquid is 5%～20% with the mol ratio as the dimethyl oxalate (DMO) of substrate.
As of the present invention
Figure BDA0000371791280000032
the improvement of the application of acid ion liquid in preparing phenyloxalate (DPO):
Figure BDA0000371791280000033
acid ion liquid be following any one:
[MimN(CH 2) 4SO 3H][HSO 4]、[(CH 3) 3N(CH 2) 4SO 3H][HSO 4]、[(C 2H 5) 3N(CH 2) 4SO 3H][HSO 4]、[MimN(CH 2) 4SO 3H][TsO]、[PyN(CH 2) 4SO 3H][HSO 4]、[PyN(CH 2) 4SO 3H][TsO]、[PyN(CH 2) 4SO 3H][MsO]、[PyN(CH 2) 4SO 3H][AcO]。
As of the present invention
Figure BDA0000371791280000034
the improvement of the application of acid ion liquid in preparing phenyloxalate (DPO): acid ion liquid is [MimN (CH 2) 4sO 3h] [HSO 4], temperature of reaction is 180, ℃ reaction times is 4h; The mol ratio of phenol and dimethyl oxalate (DMO) is 10.0:1; As catalyzer acid ion liquid is 10% with the mol ratio as the dimethyl oxalate (DMO) of substrate.
In the present invention:
Figure BDA0000371791280000037
the preparation method reference of acid ion liquid (1. Liu Xiu plum, Jiang Xiao, Wang Chang. the research [R] of the synthetic and catalytic performance of trimethylamine groups azochlorosulfonate acid ion liquid. Qingdao: China University Of Petroleum Beijing, 2007.; 2. yellow precious magnificent, Wang Yanfei, Du Zhifei. the synthetic and spectral characterization [J] of acidic ion liquid. analytical test journal, 2007,26 (4): 478-483.), under condition of no solvent, N-Methylimidazole is added dropwise to 1,4-butane sultone, it is intermediate N (4-sulfonic group) butyl-imidazole salts that reacting by heating obtains white solid, and the latter is suspended in hexanaphthene, adds the vitriol oil of equimolar amount under normal temperature, temperature reaction, finally removes excessive moisture and can obtain ionic liquid [MimN (CH 2) 4sO 3h] [HSO 4].Adopt similar method can obtain the ionic liquid of a series of other kinds-- acid ion liquid, described in
Figure BDA0000371791280000039
molecular formula and the structural formula of acid ion liquid are as shown in table 1.
The numbering of table 1 ionic liquid, molecular formula and structure
Figure BDA00003717912800000310
Figure BDA0000371791280000041
Particularly:
One, ionic liquid [MimN (CH 2) 4sO 3h] [HSO 4] preparation, carry out successively following steps:
Under condition of no solvent, first add 15mL1,4-butyl sultone is in 100mL there-necked flask, under normal temperature, in 15min, drip gradually 10mL N-Methylimidazole, be heated to 40 ℃, stir 12h, obtain white solid, use 20mL toluene wash, then suction filtration in triplicate, is dried (90 ℃ by the solid obtaining in vacuum drying oven, 0.01MPa), gained white powder is intermediate N (4-sulfonic group) butyl-imidazole salts (yield 81.6%).Taking 10g intermediate adds in 100mL there-necked flask, add 25mL hexanaphthene to make its suspension, under magnetic agitation, under normal temperature, be added dropwise to 98%(massfraction) vitriol oil 1.8mL, about 5min, dropwise rear slow intensification (completing intensification for 20min minute) to 80 ℃, reaction 6h, after reaction finishes, utilize Rotary Evaporators to remove unnecessary moisture and solvent hexanaphthene, obtain thick liquid [MimN (CH 2) 4sO 3h] [HSO 4], be placed in vacuum drying oven dry (90 ℃, 0.01MPa), yield 98.5%.Gained ionic liquid [MimN (CH 2) 4sO 3h] [HSO 4] be placed in moisture eliminator and preserve.
Change the N-Methylimidazole in above-mentioned preparation method into triethylamine, all the other are constant, obtain ionic liquid IL2.
Change the N-Methylimidazole in above-mentioned preparation method into Trimethylamine 99, all the other are constant, obtain ionic liquid IL3.
Change the sulfuric acid in above-mentioned preparation method into p-methyl benzenesulfonic acid, all the other are constant, obtain ionic liquid IL4.
Change the N-Methylimidazole in above-mentioned preparation method into pyridine, all the other are constant, obtain ionic liquid IL5.
Change the N-Methylimidazole in above-mentioned preparation method into pyridine, sulfuric acid changes p-methyl benzenesulfonic acid into, and all the other are constant, obtains ionic liquid IL6.
Change the N-Methylimidazole in above-mentioned preparation method into pyridine, sulfuric acid changes methylsulfonic acid into, and all the other are constant, obtains ionic liquid IL7.
Change N-Methylimidazole in above-mentioned preparation method into pyridine, sulfuric acid changes acetic acid into, and all the other are constant, obtains ionic liquid IL8.
Reaction of the present invention can be carried out in 250mL there-necked flask, on there-necked flask, sealed stirrer is housed, temperature is taken into account straight cold finger.Under normal pressure, add quantitative phenol, DMO and ionic-liquid catalyst----
Figure BDA0000371791280000051
acid ion liquid, stirs and heats up.In reflux condensing tube, pass into 80 ℃ of thermostatical circulating waters, in cold-trap, collect overhead product (be mainly raw material dimethyl oxalate (DMO) that boiling point is lower and as the products such as methyl-phenoxide of by product).Cold-trap outlet connects T-valve, gets the analysis of gas sample at T-valve place.Reaction finishes rear standing separatory (thereby obtaining the ionic-liquid catalyst that is positioned at lower floor and the organic layer that is positioned at upper strata), isolated ionic-liquid catalyst Recycling, organic layer is the mixture of reaction product and unreacting material, by gas chromatographic analysis, determines that reaction solution (organic layer of standing separatory gained), liquid overhead product (in cold-trap collected overhead product) and gaseous sample (the gas sample that get in T-valve place) form.
GC conditions: 250 ℃ of gasification temperatures, nitrogen is done carrier gas, presses 60kPa before post, split stream sampling, splitting ratio 50:1, post flow 1.0mL/min, column temperature is taked 35 ℃ of constant temperature, and after liquid overhead product and standing separatory, gained organic layer merges rear direct injection, and sample size is 0.1 μ L.
Remarks explanation:
1, owing to containing the high-melting-point substances such as phenol in overhead product, if select normal temperature recirculated water, easily cause in prolong and solidify, therefore selected 80 ℃ of thermostatical circulating waters.
2, after liquid overhead product and standing separatory, after the merging of gained organic layer, detecting is in order to determine that the transformation efficiency of raw material dimethyl oxalate (DMO) is, selectivity and the yield of each product, analyzing the gas of getting in T-valve place is in order to guarantee that all raw materials and product are all condensed, and not volatilization; That is, it is to be all condensed and not escape in order to ensure all components relevant with reaction that collection gaseous sample detects, thereby guarantees the accuracy of reaction preference and yield.
Technical scheme of the present invention is specific as follows:
1) under condition of no solvent, prepare a series of acid ion liquid; 2) in 250mL there-necked flask, carry out the reaction of the synthetic DPO of phenol and DMO transesterify, on there-necked flask, sealed stirrer is housed, temperature is taken into account straight cold finger.Under normal pressure, add quantitative phenol, DMO and ionic-liquid catalyst, stir and heat up.In reflux condensing tube, pass into 80 ℃ of thermostatical circulating waters, in cold-trap, collect overhead product.Cold-trap outlet connects T-valve, gets the analysis of gas sample at T-valve place.Reaction finishes rear standing separatory and isolates ionic-liquid catalyst Recycling, and organic layer is the mixture of reaction product and unreacting material, by gas chromatographic analysis, determines reaction solution, liquid overhead product and gas sample composition.According to the quality of product in overhead product and reaction flask and composition, calculate whole reaction conversion ratio, selectivity and yield.
The present invention utilizes
Figure BDA0000371791280000053
acid ion liquid catalyst phenol and dimethyl oxalate carry out transesterification reaction, and tool has the following advantages:
1, in contrast to homogeneous catalysis system, this catalyst system have catalyst separating simple, can be recycled, the advantage such as equipment corrosion is little, react more green close friend;
2, in contrast to existing heterogeneous catalysis system, this catalyst system have cost of material relatively cheap, easy to prepare, be convenient to the advantages such as preservation.
Embodiment
Embodiment 1,
Figure BDA0000371791280000061
the application of acid ion liquid in preparing phenyloxalate (DPO), with
Figure BDA0000371791280000062
acid ion liquid [(CH 3) 3n (CH 2) 4sO 3h] [HSO 4] be catalyzer (hereinafter to be referred as ionic-liquid catalyst), carry out successively following steps:
Sealing machine agitator is housed, temperature is taken into account in the 250mL there-necked flask of reflux condensing tube, adds phenol 47.5g(0.5mol under normal pressure), DMO11.8g(0.1mol) and ionic-liquid catalyst [(CH 3) 3n (CH 2) 4sO 3h] [HSO 4] 1.5g(5mmol), stir and heat up.In reflux condensing tube, pass into 80 ℃ of thermostatical circulating waters, in cold-trap, collect overhead product (be mainly raw material dimethyl oxalate (DMO) that boiling point is lower and as the products such as methyl-phenoxide of by product).Cold-trap outlet connects T-valve, gets the analysis of gas sample at T-valve place.Controlling temperature of reaction is 160 ℃, and the reaction times is 2h, reaction finishes rear standing separatory (thereby obtaining the ionic-liquid catalyst that is positioned at lower floor and the organic layer that is positioned at upper strata), the Recycling of isolated ionic-liquid catalyst energy, organic layer be reaction product (, phenyloxalate, methyl-phenoxide and methyl phenyl oxalate as by product) and unreacting material is (, phenol and dimethyl oxalate) mixture, by gas chromatographic analysis, determine reaction solution (organic layer of standing separatory gained), liquid overhead product (in cold-trap collected overhead product) and gaseous sample (the gas sample that get in T-valve place) form.GC conditions is with mentioned above.The results are shown in Table 2.
Remarks explanation: yield is for dimethyl oxalate.
Embodiment 2～14, for embodiment 1, change phenol consumption, catalyzer and consumption, temperature of reaction, reaction times; Obtain embodiment 2～14; The result of gained is as described in Table 2.
Table 2
Figure BDA0000371791280000063
Note: dimethyl oxalate (DMO), phenyloxalate (DPO), methyl phenyl oxalate (MPO)--by product.
Comparative example 1～3, by the catalyzer in embodiment 12 make into reference [1) Liu, Y.; Zhao, G.; Zhu, W.; Wang, J.; Liu, G.; Zhang, W.; Jia, M.Journal Of The Brazilian Chemical Society2010,21,2254-2261.; 2) Gong Jinlong. loading type MoO 3the research [D] of catalysis dimethyl oxalate and phenol ester permutoid reaction synthesis of oxalic acid diphenyl ester. University Of Tianjin, 2004.; 3) Wang Shengping. phenol and dimethyl oxalate synthesis of diphenyl carbonate by ester exchange reaction [D]. University Of Tianjin, 2003.] described catalyzer, all the other are all equal to embodiment 12.The result of gained is as described in Table 3.
Table 3
Figure BDA0000371791280000072
Figure BDA0000371791280000081
Remarks explanation:
The mesopore molecular sieve AEP-MCM-41 that comparative example 1 used catalyst is amido functional group,
Comparative example 2 used catalysts are 1%MO 3/ SiO 2loaded catalyst,
Comparative example 3 used catalysts are 10%TiO 2/ SiO 2loaded catalyst.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.

Claims (3)

1.
Figure FDA0000371791270000011
the application of acid ion liquid in preparing phenyloxalate, is characterized in that: phenol and dimethyl oxalate exist
Figure FDA0000371791270000012
under the katalysis of acid ion liquid, carry out transesterification reaction, described transesterification reaction is carried out under condition of no solvent, and temperature of reaction is 150～250 ℃, and the reaction times is 2～5h, must contain the mixture of phenyloxalate;
The mol ratio of phenol and dimethyl oxalate is 2.0～10.0:1;
As catalyzer acid ion liquid is 5%～20% with the mol ratio as the dimethyl oxalate of substrate.
2. according to claim 1
Figure FDA0000371791270000014
the application of acid ion liquid in preparing phenyloxalate, is characterized in that: described in
Figure FDA0000371791270000015
acid ion liquid be following any one:
[MimN(CH 2) 4SO 3H][HSO 4]、[(CH 3) 3N(CH 2) 4SO 3H][HSO 4]、[(C 2H 5) 3N(CH 2) 4SO 3H][HSO 4]、[MimN(CH 2) 4SO 3H][TsO]、[PyN(CH 2) 4SO 3H][HSO 4]、[PyN(CH 2) 4SO 3H][TsO]、[PyN(CH 2) 4SO 3H][MsO]、[PyN(CH 2) 4SO 3H][AcO]。
3. according to claim 2
Figure FDA0000371791270000016
the application of acid ion liquid in preparing phenyloxalate, is characterized in that: described in
Figure FDA0000371791270000017
acid ion liquid is [MimN (CH 2) 4sO 3h] [HSO 4], temperature of reaction is 180, ℃ reaction times is 4h; The mol ratio of phenol and dimethyl oxalate (DMO) is 10.0:1; As catalyzer acid ion liquid is 10% with the mol ratio as the dimethyl oxalate (DMO) of substrate.
CN201310374161.2A 2013-08-26 2013-08-26 Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate Active CN103524341B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310374161.2A CN103524341B (en) 2013-08-26 2013-08-26 Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310374161.2A CN103524341B (en) 2013-08-26 2013-08-26 Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate

Publications (2)

Publication Number Publication Date
CN103524341A true CN103524341A (en) 2014-01-22
CN103524341B CN103524341B (en) 2014-12-24

Family

ID=49926751

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310374161.2A Active CN103524341B (en) 2013-08-26 2013-08-26 Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate

Country Status (1)

Country Link
CN (1) CN103524341B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105198745A (en) * 2015-09-25 2015-12-30 中建安装工程有限公司 Method and device for preparing diphenyl carbonate by means of catalyzed transesterification by aid of ionic liquid
CN105198746A (en) * 2015-10-14 2015-12-30 中建安装工程有限公司 Method and device for preparing diphenyl carbonate by using phenol and dimethyl carbonate through one-step method
CN105348092A (en) * 2015-09-29 2016-02-24 西安嘉宏能源化工科技有限公司 Oxalate preparation process and application thereof
CN116393167A (en) * 2023-03-09 2023-07-07 新疆至臻化工工程研究中心有限公司 Ionic liquid catalyst for transesterification of dimethyl oxalate and ethanol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412176A (en) * 2002-08-28 2003-04-23 天津大学 Method for preparing methyl phenyl oxalate and phenostal
CN1412178A (en) * 2002-08-28 2003-04-23 天津大学 Preparation method of methyl phenyl oxalate and phenostal
CN1562952A (en) * 2004-04-08 2005-01-12 天津大学 Method for catalyzer synthesizing methyl-phenyl-oxalate and phenostal
CN102029187A (en) * 2008-01-02 2011-04-27 吉林大学 Organic base catalyst for synthesizing aryl carboxylate through ester exchange

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412176A (en) * 2002-08-28 2003-04-23 天津大学 Method for preparing methyl phenyl oxalate and phenostal
CN1412178A (en) * 2002-08-28 2003-04-23 天津大学 Preparation method of methyl phenyl oxalate and phenostal
CN1562952A (en) * 2004-04-08 2005-01-12 天津大学 Method for catalyzer synthesizing methyl-phenyl-oxalate and phenostal
CN102029187A (en) * 2008-01-02 2011-04-27 吉林大学 Organic base catalyst for synthesizing aryl carboxylate through ester exchange

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
侯丽伟: "Bronsted酸性离子液体催化大豆油脂交换反应", 《中国优秀硕士学位论文全文数据库工程科技I辑》, 15 January 2010 (2010-01-15), pages 016 - 248 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105198745A (en) * 2015-09-25 2015-12-30 中建安装工程有限公司 Method and device for preparing diphenyl carbonate by means of catalyzed transesterification by aid of ionic liquid
CN105198745B (en) * 2015-09-25 2017-07-28 中建安装工程有限公司 A kind of ionic liquid-catalyzed ester exchange reaction prepares the method and device of diphenyl carbonate
CN105348092A (en) * 2015-09-29 2016-02-24 西安嘉宏能源化工科技有限公司 Oxalate preparation process and application thereof
CN105198746A (en) * 2015-10-14 2015-12-30 中建安装工程有限公司 Method and device for preparing diphenyl carbonate by using phenol and dimethyl carbonate through one-step method
CN105198746B (en) * 2015-10-14 2017-08-04 中建安装工程有限公司 A kind of phenol and dimethyl carbonate one-step method prepares the method and device of diphenyl carbonate
CN116393167A (en) * 2023-03-09 2023-07-07 新疆至臻化工工程研究中心有限公司 Ionic liquid catalyst for transesterification of dimethyl oxalate and ethanol

Also Published As

Publication number Publication date
CN103524341B (en) 2014-12-24

Similar Documents

Publication Publication Date Title
Wang et al. Novel Brønsted acidic ionic liquids based on benzimidazolium cation: Synthesis and catalyzed acetalization of aromatic aldehydes with diols
Aresta et al. Valorization of bio-glycerol: New catalytic materials for the synthesis of glycerol carbonate via glycerolysis of urea
CN103524341B (en) Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate
JP5958549B2 (en) Method for producing diethyl carbonate
Li et al. Synthesis of dimethyl carbonate from methanol, propylene oxide and carbon dioxide over KOH/4A molecular sieve catalyst
CN109174176B (en) Basic ionic liquid catalyst and preparation method thereof
CN102516128B (en) Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis
CN103497082B (en) A kind of method preparing beta-nitrostyrene and derivative thereof
Wang et al. A benign preparation of sec-butanol via transesterification from sec-butyl acetate using the acidic Imidazolium ionic liquids as catalysts
CN104030975B (en) A kind of Mn (III)-Salen Catalysts and its preparation method and application
US20070232824A1 (en) Heterogeneous catalysis solid base catalyst and a preparation process and a use thereof
Chaves et al. A selective synthesis of glycerol carbonate from glycerol and urea over Sn (OH) 2: A solid and recyclable in situ generated catalyst
CN102000559A (en) Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst
Shaterian et al. Ionic-liquid-catalyzed green synthesis of coumarin derivatives under solvent-free conditions
Xiao et al. Transesterification of dimethyl carbonate and phenol to diphenyl carbonate with the bismuth compounds
CN103524478B (en) Device and method for shortening ketalation time in ibuprofen synthesis process
CN102397793A (en) Quinine-squaric acid amide hydrogen bond catalysts, synthesis method, and application of quinine-squaric acid amide hydrogen bond catalysts in asymmetrical reactions
Ma et al. A comparative study of supported TiO2 catalysts and activity in ester exchange between dimethyl oxalate and phenol
Janus et al. Chiral protic imidazolium salts with a (−)-menthol fragment in the cation: synthesis, properties and use in the Diels–Alder reaction
CN105032473B (en) A kind of method using the sulfuric acid modified catalyst preparation dialkoxy methanes for the treatment of nanoscale HZSM 5
CN111377891B (en) Device and method for preparing 2,5-furandicarboxylic acid from hexoic acid (salt) by coupling dehydration cyclization and azeotropic distillation water removal
Mennecke et al. Immobilization of NHC-Bearing Palladium Catalysts on Polyvinylpyridine; Applications in Suzuki-Miyaura and Hartwig-Buchwald Reactions under Batch and Continuous-Flow Conditions
CN111701621B (en) Synthesis of coordination type zirconium o-benzenetrisol and application of coordination type zirconium o-benzenetrisol in preparation of cyclohexanol
JP2004018378A (en) Catalyst for producing ether compound, method for producing ether compound using the same catalyst and ether compound obtained by the same method for production
Shen et al. Stable Organic Titanium Catalysts and Reactive Distillation Used for the Transesterification of Dimethyl Carbonate with Phenol

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: 210046 Wen Lan Road, Qixia District, Nanjing, Jiangsu Province, No. 6

Co-patentee after: Zhejiang University

Patentee after: China Construction Installation Group Co., Ltd.

Address before: 210046 No. 100, Yaohua Menyao'an New Village, Qixia District, Nanjing City, Jiangsu Province

Co-patentee before: Zhejiang University

Patentee before: China Construction Industrial Equipment Installation Co., Ltd.