CN106699562A - Process for producing diphenyl carbonate by non-solvent method - Google Patents

Abstract

The object of the invention is to provide a process for producing diphenyl carbonate by a non-solvent method. The process can be used for reducing product production cost and waste discharge while improving product quality. The process comprises the steps: melting phenol, and heating the temperature of the melted phenol to 110 DEG C to 130 DEG C; adding DMF or N,N-dimethylaniline or an analog of the DMF or N,N-dimethylaniline, which serves as a catalyst, into the melted phenol in accordance with that the added amount of the catalyst is 0.03% to 3% that of the phenol; maintaining the temperature, introducing phosgene with stirring, and carrying out a photochemical reaction; then, heating to a temperature of 140 DEG C to 180 DEG C, and carrying out heat preservation for 1 to 5 hours; and then, carrying out reduced-pressure distillation, thereby obtaining a product. According to the new process provided by the invention, the quality and yield of the product are improved, meanwhile, sodium chloride mother liquor and wastewater are thoroughly avoided, distillation residues are reduced, the production cost is reduced, and clean production is achieved. Recovering operation of a phenol system, a special batching procedure and the like are reduced, and the production efficiency is increased greatly; and the operation is more stable, and the safety of production is improved.

Description

The technique that non-solvent method produces diphenyl carbonate

Technical field

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

Background technology

Diphenyl carbonate (DPC) is a kind of water insoluble, is dissolved in hot ethanol, benzene, ether, carbon tetrachloride, glacial acetic acid Deng the white crystalline solid of organic solvent.It is mainly used in the synthesis of engineering plastics makrolon and ekonol etc. Raw material, it is also possible to plasticizer and solvent as nitrocellulose.It is mainly used in synthesizing methyl isocyanate on agricultural chemicals, enters And prepare carbamate insecticides carbofuran.In addition it is mainly used in plastics industry, manufactures poly- aryl carbonates and to hydroxyl Yl benzoic acid polyester, monoisocyanates, diisocyanate.Plastic plasticizer can also be prepared.It is used as in Chemical Manufacture molten Agent and thermophore.

The production of diphenyl carbonate in the prior art is mainly with phenol as raw material, with phosgene reaction under alkaline solution medium, 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 defect of the technique is：Synthesis procedure is cumbersome, produces substantial amounts of sodium chloride mother liquid coming, Difficult treatment；And product quality is not high, appearance color is unstable, occurs light yellow, light green color, pale red often；Return Kettle distills, and during consumption energy consumption, high cost, 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 the technique that a kind of non-solvent method produces diphenyl carbonate, and the technique can improve 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 diphenyl carbonate Technique, step includes：

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

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

Phosgene is passed through under keeping temperature, stirring condition carries out photochemical reaction；

Then heat to 140-180 DEG C and be incubated 1-5 hours；

Then vacuum distillation obtains product.

Preferably, described phosgene is slowly continuously passed through in phenol, is passed through speed to be free of phosgene in the tail gas for reacting generation It is degree.

Preferably, described reaction system phenol content ＜ 5%, phenyl chloroformate content ＜ 1.5% are photochemical reaction terminal.

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

Preferably, described 140-180 DEG C of 3-5 hour of insulation of reaction system.Or described reaction system is to chloro-carbonic acid 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, 220 DEG C of oil temperature, 190 DEG C of interior temperature, vacuum to be more than Equal to 0.095Mpa.

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

Advantageous Effects of the invention：

1st, dpc production new technology improves product quality and yield, at the same thoroughly avoid sodium chloride mother liquid coming and Waste water, bottoms are reduced, reduce production cost, accomplished clean manufacturing.

2nd, operation, special burden process of phenol system recovery etc. are reduced, production efficiency is greatly improved；Simplify Operation.

3rd, new technology makes diphenyl carbonate operate more steadily, 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.

Specific embodiment

Technical scheme is described further below：Non-solvent method of the invention produces the technique of diphenyl carbonate, step Suddenly include：

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

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 carries out photochemical reaction；As long as it is anti-to be passed through phosgene with this understanding Product should be obtained, phenol redistillation is then peeled off and be can be obtained by product.

In order that must react more completely, preferred mode of operation is：Phosgene is slowly continuously passed through in phenol, is passed through speed to react It is degree that phosgene is free of in the tail gas of generation.Then sustained response, until described reaction system phenol content ＜ 5%, chloro-carbonic acid benzene Ester content ＜ 1.5% is photochemical reaction terminal.Generally, described phenol and the molar ratio of phosgene are 1 (0.6-0.9).

Then heat to 140-180 DEG C and be incubated 1-5 hours；

Preferably：Described 140-180 DEG C of 3-5 hour of insulation of reaction system；Or described reaction system is to chloro-carbonic acid benzene Ester 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 obtained using oil bath heating vacuum distillation, 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 technological thought of the invention, several groups of preferred embodiments are provided below, But implementation of the invention is not limited only to following examples.

Embodiment 1

Phenol 282g is put into 500ml reaction bulbs, heat up melting, when reaching 115 DEG C, 1% addition by phenol weight is appropriate Catalyst DMF.Flow is controlled to be slowly introducing phosgene under stirring condition, it is ensured 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 phosgene reality The mol ratio that border uses is 1:0.8.It is warmed up to 150 DEG C and is incubated 3 hours, measures phenyl chloroformate content ＜ 0.1% for terminal.Adopt Use oil bath heating distillation technique, 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.

Embodiment 2

Phenol 282g is put into 500ml reaction bulbs, heat up melting, when reaching 115 DEG C, 1.1% addition by phenol weight is appropriate Catalyst n, accelerine.Flow is controlled to be slowly introducing phosgene under stirring condition, it is ensured that phosgene reaction is complete；When photochemical Between 13 hours, 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, measure phenyl chloroformate content ＜ 0.1% for terminal.Phenol is actually used with phosgene Mol ratio is 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, heat up melting, when reaching 115 DEG C, 1.1% addition by phenol weight is suitable Amount catalyst DMF.Flow is controlled to be slowly introducing phosgene under stirring condition, it is ensured that phosgene reaction is complete；The photochemical time 11 is small When, sampling analysis：Phenol 5.8%, phenyl chloroformate 0.3%, diphenyl carbonate 92.3%, reaction terminates；Phenol and phosgene reality The mol ratio that border uses is 1:0.6.It is warmed up to 160 DEG C and is incubated 4 hours, measures phenyl chloroformate content ＜ 0.1% for terminal.Adopt Use 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, 190 DEG C of interior temperature, vacuum 0.097Mpa, distill to obtain product.

Claims (3)

1. a kind of non-solvent method produces the technique of diphenyl carbonate, and step includes：Phenol 282g is put into 500ml reaction bulbs, heat up melting, when reaching 115 DEG C, by 1% addition proper catalyst DMF of phenol weight；Flow is controlled to be slowly introducing phosgene under stirring condition, it is ensured that phosgene reaction is complete；Photochemical to 12 hours, sampling analysis：Phenol 2.1%, phenyl chloroformate 0.9%, diphenyl carbonate 96.3%, reaction terminates；It is warmed up to 150 DEG C and is incubated 3 hours, measures phenyl chloroformate content ＜ 0.1% for terminal；Using oil bath heating distillation technique.

2. the technique that a kind of non-solvent method according to claim 1 produces diphenyl carbonate, it is characterised in that the phenol is 1 with the actually used mol ratio of phosgene:0.8.

3. the technique that a kind of non-solvent method according to claim 1 produces diphenyl carbonate, 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.