阅读说明：本技术 一种二苯基氯化膦的制备方法 (Preparation method of diphenyl phosphine chloride ) 是由 何子健 于 2019-09-30 设计创作，主要内容包括：本发明的一种二苯基氯化膦的制备方法,属于化学合成技术领域,该方法首先将苯和三氯化铝投入反应釜中,搅拌下向釜中加入三氯化磷,缓慢升温至120℃,反应12 h。关闭加热降温至60℃,分批加入解络剂,升温至80℃搅拌2 h。脱溶完毕后精馏分离出一苯基二氯化膦和二苯基氯化膦,精馏完成,适当降温后将残留液体缓慢加入20%的盐酸溶液中,搅拌2 h,离心得解络剂湿品和氯化铝溶液,湿品解络剂干燥后可以循环使用,氯化铝溶液用来制备絮凝剂。本发明使用新的解络剂,解决生产二苯基氯化膦的固废问题,降低了生产成本,使产品具有市场竞争力。(The invention relates to a preparation method of diphenyl phosphine chloride, which belongs to the technical field of chemical synthesis. And (3) closing the heating and cooling to 60 ℃, adding the decomplexing agent in batches, heating to 80 ℃, and stirring for 2 hours. And after the desolventizing is finished, rectifying to separate the phenylphosphonic dichloride and the diphenylphosphine chloride, after the rectification is finished, slowly adding the residual liquid into a 20% hydrochloric acid solution after proper temperature reduction, stirring for 2 hours, and centrifuging to obtain a decomplexer wet product and an aluminum chloride solution, wherein the wet product decomplexer can be recycled after being dried, and the aluminum chloride solution is used for preparing the flocculant. The invention uses the new decomplexer, solves the solid waste problem of producing diphenyl phosphine chloride, reduces the production cost and ensures that the product has market competitiveness.)

1. A preparation method of diphenyl phosphine chloride comprises the following steps:

a. synthesis of diphenyl phosphine chloride

Mixing benzene and aluminum trichloride, adding phosphorus trichloride under the condition of stirring, heating to 120 ℃ at the heating rate of 100 ℃/h, reacting for 12h, and cooling to 60 ℃ to obtain a product A;

b. relieving the obstruction in the channels

Mixing the product A prepared in the step a with a decomplexing agent, stirring for 2 hours at 80 ℃, rectifying at-0.1 MPa and 130 ℃, collecting the mono-phenyl phosphine dichloride, heating to 200 ℃, collecting the diphenyl phosphine chloride which is a target product, and simultaneously obtaining a residual liquid B;

c. recovering

And c, cooling the residual liquid B obtained in the step B to 50 ℃, adding a hydrochloric acid solution with the mass concentration of 20% into the residual liquid, stirring for 2 hours, centrifuging to obtain a wet decomplexer and an aluminum chloride solution, and recycling the dried wet decomplexer and the aluminum chloride solution.

2. The method according to claim 1, wherein the method comprises the following steps: the molar ratio of benzene to phosphorus trichloride to aluminum trichloride is (1-3): 1: (0.25 to 1.5).

3. The method according to claim 1, wherein the method comprises the following steps: the decomplexer is one or a combination of more of triethyl phosphine oxide, triphenyl phosphine oxide and tricyclohexyl phosphine oxide in any proportion.

4. The process according to claim 1 or 3, characterized in that: the dosage of the decomplexer is 80 to 150 percent of the molar percentage of the phosphorus trichloride.

5. The method according to claim 1 or 3, wherein the mass ratio of the raffinate B to the hydrochloric acid in the step c is 1: 1 to 3.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of diphenyl phosphine chloride.

Background

Diphenyl phosphine chloride is an important intermediate for producing a photoinitiator TPO, and currently, the method for industrially synthesizing diphenyl phosphine chloride is to generate phenyl phosphine chloride by utilizing benzene and phosphorus trichloride under the action of Lewis acid, then to obtain the diphenyl phosphine chloride by disproportionation reaction and decomplexation by taking potassium chloride, sodium chloride, cyclic ether, phosphorus oxychloride and the like as decomplexers.

In order to solve the above problems, the prior art generally adopts the replacement of the catalyst or the replacement of the decomplexing agent to solve the problems.

Patent publication No. CN102942591A reports that the preparation of diphenyl phosphonium chloride by using Lewis acid room temperature ionic liquid as a catalyst has high cost, and in the report, the ionic liquid can be recycled, but the recycling is complicated, and the application frequency is limited.

Patent publication No. CN102399243A reports the preparation of diphenyl phosphonium chloride using triethyl beta-chlorophosphonate as decomplexer. The substance after decomplexation by the decomplexer is separated by liquid separation, but a large amount of organic solvent is used in the synthesis process, and the decomplexer cannot be recovered.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a preparation method of diphenyl phosphine chloride, which comprises the steps of synthesizing diphenyl phosphine chloride by reacting benzene and phosphorus trichloride in the presence of aluminum trichloride, further using one or more of triethyl phosphine oxide, triphenyl phosphine oxide and dicyclohexyl phosphine oxide as a decomplexer, and using the reaction liquid after decomplexation as a liquid so as to solve the problem of high difficulty in solid-liquid distillation in the past; meanwhile, the decomplexer can be recycled, so that the generation of solid wastes is avoided, the cost is reduced, and the product has market competitiveness.

The invention is realized by the following technical scheme:

a preparation method of diphenyl phosphine chloride comprises the following steps:

a. synthesis of diphenyl phosphine chloride

Mixing benzene and aluminum trichloride, adding phosphorus trichloride under the condition of stirring, heating to 120 ℃ at the heating rate of 100 ℃/h, reacting for 12h, and cooling to 60 ℃ to obtain a product A;

b. relieving the obstruction in the channels

Mixing the product A prepared in the step a with a decomplexing agent, stirring for 2 hours at 80 ℃, rectifying at-0.1 MPa and 130 ℃, collecting the mono-phenyl phosphine dichloride, heating to 200 ℃, collecting the diphenyl phosphine chloride which is a target product, and simultaneously obtaining a residual liquid B;

c. recovering

And c, cooling the residual liquid B obtained in the step B to 50 ℃, adding a hydrochloric acid solution with the mass concentration of 20% into the residual liquid, stirring for 2 hours, centrifuging to obtain a wet decomplexer and an aluminum chloride solution, and recycling the dried wet decomplexer and the aluminum chloride solution.

As a further improvement of the invention, the molar ratio of benzene to phosphorus trichloride to aluminum trichloride is (1-3): 1: (0.25 to 1.5).

As a further improvement of the invention, the decomplexer is one or a combination of more of triethyl phosphine oxide, triphenyl phosphine oxide and tricyclohexyl phosphine oxide in any proportion.

As a further improvement of the invention, the dosage of the decomplexer is 80 to 150 mole percent of the dosage of the phosphorus trichloride.

As a further improvement of the invention, the mass ratio of the raffinate B to the hydrochloric acid in the step c is 1: 1 to 3.

Adopt above-mentioned technical scheme's positive effect: in the preparation process of the diphenyl phosphine chloride, the novel complexing agent is used, so that the problems of difficult distillation, environmental pollution and high cost in the conventional synthesis process are solved, the reaction yield is improved, and the yield of the diphenyl phosphine chloride is up to over 72 percent.

Detailed Description

The invention is further illustrated with reference to the following specific examples, which should not be construed as limiting the invention thereto.