CN108203381A - The technique that non-solvent method produces diphenyl carbonate - Google Patents

Abstract

The object of the present invention is to provide a kind of techniques of non-solvent method production diphenyl carbonate, which can improve product quality reduces production cost and waste discharge simultaneously；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；Temperature is kept, phosgene is passed through under stirring condition and carries out photochemical reaction；It then heats to 140 180 DEG C and keeps the temperature 15 hours；Then it is evaporated under reduced pressure to product.The new process of the present invention improves product quality and yield, while thoroughly avoid sodium chloride mother liquid coming and waste water, reduce bottoms, reduces production cost, has accomplished clean manufacturing.Reduce the running of phenol system recycling, 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 for 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 for synthesizing methyl isocyanate, and then prepare ammonia on pesticide Carbamate insecticides carbofuran.In addition it is mainly used for plastics industry, manufactures poly- aryl carbonates and P-hydroxybenzoic acid gathers 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；It will Crude product high vacuum distillation, obtains product.The defects of technique is：Synthesis procedure is cumbersome, generates a large amount 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, energy consumption It takes, of high cost, production capacity is low, and the market competitiveness is weak.

Invention content

The main object of the present invention is to provide a kind of technique of non-solvent method production diphenyl carbonate, which 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 the analog of DMF or N, accelerine or the two, inventory is the 0.03-3% of phenol；

Temperature is kept, phosgene is passed through under stirring condition and carries out photochemical reaction；

It then heats to 140-180 DEG C and keeps the temperature 1-5 hours；

Then it is evaporated under reduced pressure to product.

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

Preferably, the reaction system phenol content ＜ 5%, phenyl chloroformate content ＜ 1.5% are whole for photochemical reaction Point.

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

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

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

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

Preferably, the vacuum distillation product uses oil bath heating, and 220 DEG C of oil temperature, 190 DEG C of interior temperature, vacuum degree 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 process 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 recycling, special burden process etc., greatly improve production efficiency；It simplifies Operation.

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

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

Specific embodiment

Technical scheme of the present invention 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 the analog of DMF or N, accelerine or 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 to enable reaction is more complete, preferred mode of operation is：Phosgene is slowly continuously passed through in phenol, be passed through speed with It reacts in the tail gas generated without phosgene to spend.Then sustained response, until the reaction system phenol content ＜ 5%, chlorine Phenyl formate content ＜ 1.5% is photochemical reaction terminal.In general, the phenol and the molar ratio of phosgene are 1 (0.6- 0.9)。

It then heats to 140-180 DEG C and keeps the temperature 1-5 hours；

Preferably：The 140-180 DEG C of 3-5 hour of heat preservation of reaction system；Or the reaction system is to chlorine Phenyl formate content ＜ 0.1% is heat preservation terminal.

Then using oil bath heating distillation technique separating phenol, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum degree 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 degree 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, it is provided below several groups 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, adds in suitable by the 1% of phenol weight Measure catalyst DMF.Flow is controlled 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 molar ratio of gas actual use is 1:0.8.It is warming up to 150 DEG C and keeps the temperature 3 hours, measure 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 degree 0.085Mpa distill separating phenol；Oil temperature 220 DEG C, 190 DEG C of interior temperature, vacuum degree 0.096Mpa, distill to obtain product.

Embodiment 2

Phenol 282g is put into 500ml reaction bulbs, heating melting when reaching 115 DEG C, is added in by the 1.1% of phenol weight Proper catalyst N, accelerine.Flow is controlled 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 kept the temperature, 170 DEG C keep the temperature 4 hours, measure phenyl chloroformate content ＜ 0.1% as terminal.Phenol is actually used with phosgene Molar ratio be 1:0.9.Using oil bath heating distillation technique, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum degree 0.086Mpa, distillation Separating phenol；220 DEG C of oil temperature, 190 DEG C of interior temperature, vacuum degree 0.096Mpa, distill to obtain product.

Embodiment 3

Phenol 282g is put into 500ml reaction bulbs, heating melting when reaching 115 DEG C, is added in by the 1.1% of phenol weight Proper catalyst DMF.Flow is controlled 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 molar ratio that border uses is 1:0.6.It is warming up to 160 DEG C and keeps the temperature 4 hours, measure phenyl chloroformate content ＜ 0.1% as terminal.It adopts With oil bath heating distillation technique, 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum degree 0.083Mpa distill separating phenol；220 DEG C of oil temperature, Interior 190 DEG C of temperature, vacuum degree 0.097Mpa, distill to obtain product.

Claims (3)

1. a kind of technique of non-solvent method production diphenyl carbonate, step include：Phenol 282g is put into 500ml reaction bulbs, is risen When reaching 115 DEG C, proper catalyst DMF is added in by the 1% of phenol weight for temperature melting；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 keeps the temperature 3 hours, measure phenyl chloroformate content ＜ 0.1% as terminal； Using oil bath heating distillation technique.

A kind of 2. technique of non-solvent method production diphenyl carbonate according to claim 1, which is characterized in that the phenol Molar 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, which is characterized in that the distillation Technique is divided into 180 DEG C of oil temperature, 150 DEG C of interior temperature, vacuum degree 0.085MPa, distills separating phenol；220 DEG C of oil temperature, 190 DEG C of interior temperature, Vacuum degree 0.096MPa distills to obtain product.