CN107868002A

CN107868002A - The technique that non-solvent method produces diphenyl carbonate

Info

Publication number: CN107868002A
Application number: CN201610852223.XA
Authority: CN
Inventors: 李辉
Original assignee: Qingdao Jiuzhou Thousand Machinery Co Ltd
Current assignee: Qingdao Jiuzhou Thousand Machinery Co Ltd
Priority date: 2016-09-26
Filing date: 2016-09-26
Publication date: 2018-04-03

Abstract

It is an object of the invention to provide a kind of technique of non-solvent method production diphenyl carbonate, the technique can improve product quality while reduce production cost and waste discharge；The step of technique, includes：Phenol is melted, is warming up to 110 130 DEG C；Catalyst is made with DMF or N, N dimethylaniline or the analog of the two, inventory is the 0.03 3% of phenol；Keeping temperature, phosgene is passed through under stirring condition and carries out photochemical reaction；Then heat to 140 180 DEG C and be incubated 15 hours；Then it is evaporated under reduced pressure to product.The new technology of the present invention improves product quality and yield, while thoroughly avoids sodium chloride mother liquid coming and waste water, reduces bottoms, reduces production cost, has accomplished clean manufacturing.Reduce the running of phenol system recovery, special burden process etc., greatly improve production efficiency；Operation is more steady, improves safety in production.

Description

The technique that non-solvent method produces diphenyl carbonate

Technical field

The present invention relates to chemical field, more particularly to the production technology of diphenyl carbonate.

Background technology

Diphenyl carbonate (DPC) is a kind of not soluble in water, and being dissolved in hot ethanol, benzene, ether, carbon tetrachloride, glacial acetic acid etc. has The white crystalline solid of solvent.It is mainly used in the synthesis material of engineering plastics makrolon and ekonol etc., It is also used as the plasticizer and solvent of nitrocellulose.It is mainly used in synthesizing methyl isocyanate on agricultural chemicals, and then prepares ammonia Carbamate insecticides carbofuran.In addition it is mainly used in plastics industry, manufactures poly- aryl carbonates and P-hydroxybenzoic acid and gather Ester, monoisocyanates, diisocyanate.Plastic plasticizer can also be prepared.It is used as solvent and thermophore in Chemical Manufacture.

The production of diphenyl carbonate is anti-with phosgene under alkaline solution medium mainly using phenol as raw material in the prior art Should, material stratification removes mother liquor after completion of the reaction, then carries out multiple cold wash and hot wash, and crude product is obtained through vacuum dehydration；Will Crude product high vacuum distillation, obtains product.The defects of technique is：Synthesis procedure is cumbersome, produces substantial amounts of sodium chloride mother liquid coming, processing It is difficult；And product quality is not high, appearance color is unstable, occurs light yellow, light green color, pale red often；Return kettle distillation, power consumption Time-consuming, cost is high, and production capacity is low, and the market competitiveness is weak.

The content of the invention

The main object of the present invention is to provide a kind of technique of non-solvent method production diphenyl carbonate, and the technique can improve production Product quality reduces production cost and waste discharge simultaneously.

For achieving the above object, the technical solution adopted in the present invention is：A kind of non-solvent method produces dipheryl carbonate The technique of ester, step include：

Phenol is melted, is warming up to 110-130 DEG C；

Catalyst is made with DMF or N, accelerine or the analog of the two, inventory is the 0.03-3% of phenol；

Keeping temperature, phosgene is passed through under stirring condition and carries out photochemical reaction；

Then heat to 140-180 DEG C of insulation 1-5 hour；

Then it is evaporated under reduced pressure to product.

Preferably, described phosgene is slowly continuously passed through in phenol, is passed through speed to react in caused tail gas and is free of light Gas is degree.

Preferably, described reaction system phenol content ＜ 5%, phenyl chloroformate content ＜ 1.5% are that photochemical reaction is whole Point.

Preferably, the molar ratio of described phenol and phosgene is 1:(0.6-0.9).

Preferably, 140-180 DEG C of 3-5 hour of insulation of described reaction system.Or described reaction system is to chloromethane Sour benzene content ＜ 0.1% is insulation terminal.

Preferably, described catalyst inventory is the 1% of phenol.

Preferably, described separating phenol uses oil bath heating distillation technique, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum More than or equal to 0.08Mpa.

Preferably, described vacuum distillation product uses oil bath heating, and 220 DEG C of oil temperature, 190 DEG C of interior temperature, vacuum are more than Equal to 0.095Mpa.

There is no the inventory of specified otherwise, content to be by weight in text.

The advantageous effects of the present invention：

1st, dpc production new technology improves product quality and yield, while thoroughly avoids sodium chloride mother liquid coming And waste water, reduce bottoms, production cost is reduced, has accomplished clean manufacturing.

2nd, reduce the running of phenol system recovery, special burden process etc., greatly improve production efficiency；Simplify Operation.

3rd, new technology makes diphenyl carbonate operation more steady, improves safety in production.

4th, the diphenyl carbonate product purity of new technology synthesis is high, outer end colour stable, white to off-white color flaky crystal.

Embodiment

Technical scheme is described further below：The work of the non-solvent method production diphenyl carbonate of the present invention Skill, step include：

Phenol is melted, is warming up to 110-130 DEG C；

Catalyst is made with DMF or N, accelerine or the analog of the two, inventory is the 0.03-3% of phenol,

It is preferred that inventory is the 1% of phenol.

110-130 DEG C of temperature is kept, phosgene is passed through under stirring condition and carries out photochemical reaction；As long as it is passed through on this condition Phosgene reaction can obtain product, and then separating phenol redistillation can be obtained by product.

In order that must react more completely, preferable mode of operation is：Phosgene is slowly continuously passed through in phenol, be passed through speed with Phosgene is free of in tail gas caused by reaction as degree.Then sustained response, until described reaction system phenol content ＜ 5%, chlorine Phenyl formate content ＜ 1.5% is photochemical reaction terminal.Generally, the molar ratio of described phenol and phosgene is 1 (0.6- 0.9)。

Then heat to 140-180 DEG C of insulation 1-5 hour；

Preferably：Described 140-180 DEG C of 3-5 hour of insulation of reaction system；Or described reaction system is to chlorine Phenyl formate content ＜ 0.1% is insulation terminal.

Then oil bath heating distillation technique separating phenol is used, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum are more than or equal to 0.08Mpa.Product is evaporated under reduced pressure to using oil bath heating, 220 DEG C of oil temperature, 190 DEG C of interior temperature, vacuum are more than or equal to 0.095Mpa。

To make those skilled in the art definitely and understanding the technological thought of the present invention, several groups are provided below preferably in fact Example is applied, but the implementation of the present invention is not limited only to following examples.

Embodiment 1

Phenol 282g is put into 500ml reaction bulbs, heating melting, when reaching 115 DEG C, added by the 1% of phenol weight suitable Measure catalyst DMF.Control flow to be slowly introducing phosgene under stirring condition, ensure that phosgene reaction is complete；Photochemical to 12 hours,

Sampling analysis：Phenol 2.1%, phenyl chloroformate 0.9%, diphenyl carbonate 96.3%, reaction terminates；Phenol and light The mol ratio of gas actual use is 1:0.8.It is warming up to 150 DEG C and is incubated 3 hours, measures phenyl chloroformate content ＜ 0.1% as eventually Point.Using oil bath heating distillation technique, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum 0.085Mpa, separated phenol；Oil temperature 220 DEG C, 190 DEG C of interior temperature, vacuum 0.096Mpa, distill to obtain product.

Embodiment 2

Phenol 282g is put into 500ml reaction bulbs, heating melting, when reaching 115 DEG C, added by the 1.1% of phenol weight Proper catalyst N, accelerine.Control flow to be slowly introducing phosgene under stirring condition, ensure that phosgene reaction is complete；It is photochemical 13 hours of time, sampling analysis：Phenol 3.7%, phenyl chloroformate 3.3%, diphenyl carbonate 92.3%；Add phenol 20g After being incubated, 170 DEG C are incubated 4 hours, and it is terminal to measure phenyl chloroformate content ＜ 0.1%.Phenol actually uses with phosgene Mol ratio be 1:0.9.Using oil bath heating distillation technique, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum 0.086Mpa, distillation Separating phenol；220 DEG C of oil temperature, 190 DEG C of interior temperature, vacuum 0.096Mpa, distill to obtain product.

Embodiment 3

Phenol 282g is put into 500ml reaction bulbs, heating melting, when reaching 115 DEG C, added by the 1.1% of phenol weight Proper catalyst DMF.Control flow to be slowly introducing phosgene under stirring condition, ensure that phosgene reaction is complete；The photochemical time is 11 small When, sampling analysis：Phenol 5.8%, phenyl chloroformate 0.3%, diphenyl carbonate 92.3%, reaction terminates；Phenol is real with phosgene The mol ratio that border uses is 1:0.6.It is warming up to 160 DEG C and is incubated 4 hours, it is terminal to measure phenyl chloroformate content ＜ 0.1%.Adopt With oil bath heating distillation technique, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum 0.083Mpa, separated phenol；220 DEG C of oil temperature, Interior 190 DEG C of temperature, vacuum 0.097Mpa, distill to obtain product.

Claims

1. a kind of technique of non-solvent method production diphenyl carbonate, step include：Phenol 282g is put into 500ml reaction bulbs, risen Temperature melting, when reaching 115 DEG C, proper catalyst DMF is added by the 1% of phenol weight；Flow is controlled slowly to lead under stirring condition Enter phosgene, ensure that phosgene reaction is complete；Photochemical to 12 hours, sampling analysis：Phenol 2.1%, phenyl chloroformate 0.9%, carbon Diphenyl phthalate 96.3%, reaction terminates；It is warming up to 150 DEG C and is incubated 3 hours, it is terminal to measure phenyl chloroformate content ＜ 0.1%； Using oil bath heating distillation technique.

A kind of 2. technique of non-solvent method production diphenyl carbonate according to claim 1, it is characterised in that the phenol Mol ratio with phosgene actual use is 1:0.8.

A kind of 3. technique of non-solvent method production diphenyl carbonate according to claim 1, it is characterised in that the distillation Technique is divided into 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum 0.085MPa, separated phenol；220 DEG C of oil temperature, 190 DEG C of interior temperature, Vacuum 0.096MPa, distill to obtain product.