CN102531908A - Preparation method of methyl phenyl carbonic ester - Google Patents
Preparation method of methyl phenyl carbonic ester Download PDFInfo
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- CN102531908A CN102531908A CN2011104493875A CN201110449387A CN102531908A CN 102531908 A CN102531908 A CN 102531908A CN 2011104493875 A CN2011104493875 A CN 2011104493875A CN 201110449387 A CN201110449387 A CN 201110449387A CN 102531908 A CN102531908 A CN 102531908A
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Abstract
The invention relates to a preparation method of methyl phenyl carbonic ester. Dimethyl carbonate and diphenyl carbonate serve as preparation raw materials. After diphenyl carbonate and a catalyst are placed in a rectification and purification reactor, the materials are slowly heated to 130-180 DEG C, dimethyl carbonate is dropwise added to the reactor slowly at the dropping speed of 0.5-15ml/ min, the temperature of reaction liquid is maintained for 1 hour, vacuum degree of the reactor is controlled to be 0.07-0.099MPa, the temperature of reaction liquid is slowly increased to 180-240 DEG C for rectification and purification, and the product of methyl phenyl carbonic ester is obtained when cut fractions at the temperature are collected. The preparation method of methyl phenyl carbonic ester can effectively resolve the problems that in the prior art, highly toxic raw materials are used, products obtained through reactions are toxic, product yield is not high, and a purification process is difficult and the like.
Description
Technical field
The invention belongs to the preparing technical field of fine chemical product, relate to a kind of method for preparing methyl benzol carbonate.
Background technology
Methyl benzol carbonate is the intermediate product of phenol and the reaction of methylcarbonate ester exchange synthesizing diphenyl carbonate; Disproportionation reaction can take place self generate diphenyl carbonate and methylcarbonate; So the yield to the ester-interchange method diphenyl carbonate synthesis has material impact, and also be an important indicator of methylcarbonate transformation efficiency.
The process method that present this area prepares methyl benzol carbonate mainly contains two kinds: the one, generate methyl benzol carbonate with phenyl chloroformate and methyl alcohol reaction; The shortcoming of this technology is: used hypertoxic phenyl chloroformate to be raw material; Also contain the toxic substance methylene dichloride in the resultant, and reacted product need pass through the washing, drying of multiple working procedure and purify after could get the higher methyl benzol carbonate of purity.Another kind of process method is to use phenol and methylcarbonate to carry out transesterification reaction and generates methyl benzol carbonate; The shortcoming of this technology is: react wayward; Methyl benzol carbonate is easy to disproportionation and generates diphenyl carbonate; And the yield of methyl benzol carbonate is very low, and reacted product need pass through, and just to obtain purity after multistep is handled be 98% methyl benzol carbonate.Except that aforesaid method; The research of p-methylphenyl carbonic ether report is less both at home and abroad at present; There is not highly purified methyl benzol carbonate product to sell on the market yet; This present situation has hindered the analysis and research work of ester exchange synthesizing diphenyl carbonate to a great extent, and therefore carrying out the highly purified methyl benzol carbonate technical study of preparation has significance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of methyl benzol carbonate, with solve the use severe toxicity raw material that exists in the prior art, resultant of reaction is poisonous, product yield is not high and problem such as purification process difficulty.
The technical solution that is used to realize the foregoing invention purpose be that to adopt mass ratio be 1: 1～5 methylcarbonate with diphenyl carbonate as preparing raw material, and prepare by following process step:
The first step, the mass ratio by 100: 0.5～10 in the rectification and purification reactor drum is put into diphenyl carbonate and catalyzer successively, mixes, and used catalyzer is Lewis acid, MOX, titanate or organic tin catalyzer;
In second step, the mixture that will pass through above step slowly is warming up to 130 ℃～180 ℃, and the rate of addition by 0.5～15ml/min slowly is added dropwise to methylcarbonate in reactor drum then;
The 3rd the step, treat that methylcarbonate dropwises after, keep reacting liquid temperature, the time is 1～10 hour;
The 4th step, the open vacuum system, with the reactor drum vacuum degree control-0.07～-0.099Mpa, slowly improve reacting liquid temperature to 180 ℃～240 ℃ and carry out rectification and purification, the cut of collecting under this temperature is the product methyl benzol carbonate.
In the technical solution of the present invention, the preferred value of the methylcarbonate that in the rectification and purification reactor drum, adds and the mass ratio of diphenyl carbonate is 1: 3; The preferred value of the mass ratio of catalyzer and diphenyl carbonate is 3: 100.
In the technical solution of the present invention, the preferred substance of catalyst system therefor is lead phenolate or tetrabutyl titanate or Dibutyltin oxide.
Preferred version of the present invention is after in the rectification and purification reactor drum, putting into diphenyl carbonate and catalyst mix material, slowly to be warming up to 150 ℃, and the rate of addition by 1.5ml/min slowly is added dropwise to methylcarbonate in reactor drum then; Keep 8 hours reacting liquid temperature time afterwards, again with the reactor drum vacuum degree control at-0.098Mpa, slowly improve reacting liquid temperature to 205 and ℃ carry out rectification and purification, the cut of collecting under this temperature is the product methyl benzol carbonate.
Compared with prior art, the beneficial effect that has of the present invention is;
One, uses that advantages of nontoxic raw materials---the present invention uses methylcarbonate and diphenyl carbonate to be raw material, avoided prior art to use hypertoxic raw material phenyl chloroformate and the safety and the problem of environmental pollution that bring.
Two, preparing product purity is high---and the methyl benzol carbonate purity of preferred preparation of the present invention can reach 99.9%, and is all higher than the methyl benzol carbonate purity of prepared in the past.
Three, preparation technology is simple---and the present invention only need can accomplish the reaction and the rectification and purification process of methyl benzol carbonate on a covering device (rectification and purification reactor drum), do not need process steps such as process washing again, drying, has simplified technological process greatly.
Embodiment
Below in conjunction with embodiment the present invention is done further description, but protection scope of the present invention is not limited to following embodiment.
Embodiment one
Get 200g diphenyl carbonate and 4g tetrabutyl titanate and add in the reactor drum, behind the reacting liquid temperature to 140 ℃ of progressively raising, slowly be added dropwise to methylcarbonate 140g, rate of addition is 1ml/min; After treating that methylcarbonate dropwises, kept reacting liquid temperature 3 hours; The open vacuum system, the reactor drum vacuum degree control slowly is increased to 220 ℃ with reacting liquid temperature and carries out rectification and purification at-0.085Mpa, collects the cut under this temperature, obtains purity and be 99.91% methyl benzol carbonate.
Embodiment two
Get 200g diphenyl carbonate and 2g Dibutyltin oxide and add in the reactor drum, behind the reacting liquid temperature to 170 ℃ of progressively raising, slowly be added dropwise to methylcarbonate 300g, rate of addition is 5ml/min; After treating that methylcarbonate dropwises, kept reacting liquid temperature 5 hours.The open vacuum system, the reactor drum vacuum degree control slowly is increased to 210 ℃ with reacting liquid temperature and carries out rectification and purification at-0.095Mpa, collects the cut under this temperature, obtains purity and be 99.93% methyl benzol carbonate.
Embodiment three
Get 200g diphenyl carbonate and 8g lead phenolate and add in the reactor drum, behind the reacting liquid temperature to 150 ℃ of progressively raising, slowly be added dropwise to methylcarbonate 270g, rate of addition is 1.5ml/min; After treating that methylcarbonate dropwises, kept reacting liquid temperature 8 hours.The open vacuum system, the reactor drum vacuum degree control slowly is increased to 205 ℃ with reacting liquid temperature and carries out rectification and purification at-0.098Mpa, collects the cut under this temperature, obtains purity and be 99.95% methyl benzol carbonate.
Claims (4)
1. the preparation method of a methyl benzol carbonate is characterized in that: to adopt mass ratio be 1: 1～5 methylcarbonate with diphenyl carbonate for preparing raw material, comprise following preparation process:
1.1 the mass ratio by 100: 0.5～10 in the rectification and purification reactor drum is put into diphenyl carbonate and catalyzer successively, mixes, used catalyzer is Lewis acid, MOX, titanate or organic tin catalyzer;
Slowly be warming up to 130 ℃～180 ℃ 1.2 will pass through the mixture of above step, the rate of addition by 0.5～15ml/min slowly is added dropwise to methylcarbonate in reactor drum then;
1.3 after treating that methylcarbonate dropwises, keep reacting liquid temperature, the time is 1～10 hour;
1.4 the open vacuum system, with the reactor drum vacuum degree control-0.07～-0.099Mpa, slowly improve reacting liquid temperature to 180 ℃～240 ℃ and carry out rectification and purification, the cut of collecting under this temperature is the product methyl benzol carbonate.
2. the preparation method of methyl benzol carbonate according to claim 1, it is characterized in that: the methylcarbonate that in the rectification and purification reactor drum, adds and the mass ratio of diphenyl carbonate are 1: 3; The mass ratio of catalyzer and diphenyl carbonate is 3: 100.
3. the preparation method of methyl benzol carbonate according to claim 1, it is characterized in that: used catalyzer is lead phenolate or tetrabutyl titanate or Dibutyltin oxide.
4. the preparation method of methyl benzol carbonate according to claim 1; It is characterized in that: after in the rectification and purification reactor drum, putting into diphenyl carbonate and catalyst mix material; Slowly be warming up to 150 ℃, the rate of addition by 1.5ml/min slowly is added dropwise to methylcarbonate in reactor drum then; Keep 8 hours reacting liquid temperature time afterwards, again with the reactor drum vacuum degree control at-0.098Mpa, slowly improve reacting liquid temperature to 205 and ℃ carry out rectification and purification, the cut of collecting under this temperature is the product methyl benzol carbonate.
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| CN201110449387.5A CN102531908B (en) | 2011-12-21 | 2011-12-21 | The preparation method of methyl benzol carbonate |
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| CN201110449387.5A CN102531908B (en) | 2011-12-21 | 2011-12-21 | The preparation method of methyl benzol carbonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467283A (en) * | 2013-09-29 | 2013-12-25 | 陕西省石油化工研究设计院 | Method for using double towers to ceaselessly compound high-purity methyl phenyl carbonic ester |
| CN109433183A (en) * | 2018-11-01 | 2019-03-08 | 河南科技学院 | A kind of bimetal composite oxide catalyst, preparation method and application |
| CN114931975A (en) * | 2022-04-13 | 2022-08-23 | 河南科技学院 | Catalyst for synthesizing diphenyl carbonate, preparation method and application of diphenyl carbonate |
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| CN1064677A (en) * | 1990-12-26 | 1992-09-23 | 旭化成工业株式会社 | Process for preparing aromatic carbonate |
| JPH10139736A (en) * | 1996-11-12 | 1998-05-26 | Mitsubishi Chem Corp | Production of alkyl aryl carbonate |
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2011
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Patent Citations (2)
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| CN1064677A (en) * | 1990-12-26 | 1992-09-23 | 旭化成工业株式会社 | Process for preparing aromatic carbonate |
| JPH10139736A (en) * | 1996-11-12 | 1998-05-26 | Mitsubishi Chem Corp | Production of alkyl aryl carbonate |
Non-Patent Citations (2)
| Title |
|---|
| 沈荣春等: "碳酸二甲酯与醋酸苯酯合成碳酸二苯酯的研究", 《石油化工》, vol. 31, no. 11, 31 December 2002 (2002-12-31), pages 897 - 900 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467283A (en) * | 2013-09-29 | 2013-12-25 | 陕西省石油化工研究设计院 | Method for using double towers to ceaselessly compound high-purity methyl phenyl carbonic ester |
| CN103467283B (en) * | 2013-09-29 | 2015-06-10 | 陕西省石油化工研究设计院 | Method for using double towers to ceaselessly compound high-purity methyl phenyl carbonic ester |
| CN109433183A (en) * | 2018-11-01 | 2019-03-08 | 河南科技学院 | A kind of bimetal composite oxide catalyst, preparation method and application |
| CN109433183B (en) * | 2018-11-01 | 2021-09-03 | 河南科技学院 | Bimetal composite oxide catalyst, preparation method and application |
| CN114931975A (en) * | 2022-04-13 | 2022-08-23 | 河南科技学院 | Catalyst for synthesizing diphenyl carbonate, preparation method and application of diphenyl carbonate |
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