SU914569A1 - Process for producing phosporus-containing polymers - Google Patents

Description

The invention relates to the chemistry of high-molecular compounds, in particular to the chemical modification of polymers with phosphorus-containing compounds, and can be used to obtain polymers that can be used in the manufacture of ion exchange resins and membranes, polymer catalysts, sorbents and transition metal ions.

A method of obtaining phosphorus-containing polymers by the interaction of a copolymer of styrene and hapogenmethyl styrene derivative with three-substituted phosphine, for example triethylphosphine, at 60 ° C in an inert gas atmosphere. According to this method, polymeric products containing salt salts of quaternary phosphonium were obtained [1].

There is also known a method for producing phosphorus-containing polymers by treating halogen-containing polymers with a metal phosphide, for example, C ^ Nurk ^ or

2

, Pk ^ Pk, in an inert solvent at a temperature from -40 to 200 ° C. The polymers obtained contain phosphine groups and are suitable as carriers for transition metal ions C2D.

The closest to the present invention is a method consisting in processing polyvinyl chloride with phosphorus trichloride in the presence of aluminum trichloride as a catalyst. The reaction is carried out using a solvent of phosphorus trichloride, at 75 ° C, for 8 hours. The resulting polymer contains 2-3.3 wt.% Phosphorus [W].

The disadvantage of this method is the duration of the reaction and the relatively high process temperature. Along with this, the resulting phosphorus-containing polymer contains a small amount of chemically bound phosphorus.

3 91456

The purpose of the invention is to increase the degree of phosphorylation and reduce the duration of the process.

The goal is achieved in that according to the process for preparing phosphorus-containing polymers by treatment with ₅ halogenated polyolefins phosphorus derivative in the presence of aluminum trichloride, phosphorus derivative as used phosphorous' vo w portly that pretreated aluminum trichloride at 70-80 ° C, and the process carried out in an inert atmosphere.

Polyvinyl chloride, copolymers of vinyl chloride with vinylidene chloride, chlorosulfonated polyethylene, trifluoroethylene and hexafluoropropylene copolymers with 20 vinylidene fluoride, polytrifluorochloroethylene can be used as halogen-containing poly-, 5 olefins. The reaction is carried out at 0-70 ° С in the medium of an organic solvent, for example, carbon tetrachloride, chlorobenzene, heptane, or without a solvent in an inert gas atmosphere.

Phosphorous hydrogen is pretreated with aluminum trichloride at 70-80 ° C. Phosphorus-containing polymer is repeatedly washed with alcohol, 30 with water and dried in an inert gas atmosphere. Replacing phosphorus trichloride with phosphorous hydrogen reduces the reaction temperature and shortens the process time. ₃ $ When a phosphorous hydrogen interacts with aluminum trichloride, a complex is formed in which the atomic orbitals of phosphine are loosened. As a result, the reaction _{40 of the} electrophilic substitution of halogen in polymers is facilitated.

Example 1. Obtaining phosphorus-containing polymer based on polyvinyl chloride without solvent. ⁴⁵

In a four-necked reactor, equipped with a mechanical stirrer, a thermometer, a gas injection bubbler, 6.7 g (0.05 mol) of anhydrous aluminum trichloride are charged and, at 75 ° C, ⁵⁰ , phosphorous is added in an argon atmosphere, which is obtained by applying dilute sulfuric acid to phosphide zinc. When the mixture begins to melt at 80 ° C, the addition of phosphorous hydrogen ⁵⁵ and the formation of the complex is considered ¹ complete. K 8.45 g of the obtained complex at 70 ° С and ne ~ 1

) four

remishivakii add 2.17 g of emulsion powdered polyvinyl chloride. The reaction mixture was stirred at 70 ° C for 1.5 hours under an argon atmosphere. Then a mixture of hydrochloric acid and ice is slowly added to the reactor while cooling with ice. The polymer in an argon atmosphere is separated by filtration, washed with water until neutral wash water, with methyl alcohol and dried under vacuum in an argon atmosphere at 60 ° C to constant weight. A powdered polymer is obtained which is insoluble in known organic solvents. The content is P 5.87% by weight; WITH

21.7 wt.%.

Example 2. Obtaining a phosphorus-containing polymer based on polyvinyl chloride in heptane.

A complex of phosphorous hydrogen with aluminum trichloride is prepared similarly to Example 1. To 11.27 g (0.067 mol) of the obtained complex, add 4C ml of dry heptane and mix until a suspension of the complex is formed. Then to the resulting suspension of the complex in heptane at 32 ° C and stirring, add 3.2 g of powdered emulsion polyvinyl chloride. The reaction mixture under argon was stirred at 32 ° C for 3 hours. Then a mixture of hydrochloric acid and ice was added to the reactor while cooling with ice. The polymer in an argon atmosphere is separated by filtration, washed with water until neutral wash water, with methyl alcohol and dried under vacuum in an argon atmosphere at 60 ° C to constant weight. A powdery, light yellow, insoluble polymer is obtained.

P content 6.63 wt.%; C 40.25 wt.%.

Example 3. Preparation of a phosphorus-containing polymer based on a copolymer of vinyl chloride with vinylidene chloride (60:40).

I

A complex of phosphorous hydrogen with aluminum trichloride is prepared analogously to example 1. To 28 g (0.14 mol) of the obtained complex at 25 ° C add 25 ml of dry chlorobenzene, and then from a dropping tube a solution of 7.7 g of copolymer in 100 ml of chlorobenzene within 2 hours. The reaction mixture is decomposed with aqueous

methanol. The polymer is separated by filtration, washed with water, methanol, and dried under vacuum to constant pressure. A pale yellow polymer insoluble in organic solvents is obtained.

Content R 8,2 wt.%.

Example 4. Obtaining phosphorus-containing polymer based on chlorine, sulfonated polyethylene.

The complex of phosphorous hydrogen with aluminum trichloride is prepared analogously to example 1, K 6.7 g

10.039 mol) of the obtained complex

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carbon tetrachloride. The reaction mixture is stirred under inert gas at 20 ° C for 1.5 hours. Then a mixture of concentrated hydrochloric acid and ice is added to the reactor. The polymer is isolated by filtration, washed with water, methanol and dried under vacuum to constant weight.

The content of P is 0.72 wt.%.

Example 7: Preparation of a phosphorus-containing polymer based on polytrifluorochloroethylene (Fluoroplast-3),

Hydrogen phosphide complex ..

add 50 mp of dry chlorobenzene, 15 with aluminum trichloride get

and then a solution of 5 g of chlorosulfonated polyethylene in 100 ml of chlorobenzene. The reaction mixture was stirred at 0 ° C for 2 hours. Then, Example I was added. To 11.3 g (0.067 mol) of the obtained complex, 40 ml of carbon tetrachloride and 2.4 g of powdered polytrifluoride with methanol were added, and poly- 20 ethylene was separated. The reaction mixture was stirred by filtration, washed with water, rolled at 20 ° under an inert atmosphere.

gas for 2 hours. Then the reaction mixture is decomposed with concentrated hydrochloric acid. The polymer is distilled and dried under vacuum to constant weight.

The content of P 2,12 wt.%.

Example 5. Preparation of phosphorus 25 by filtration, washed with water,

containing polymer based on copolymer of trifluorochloroethylene and vinylidene fluoride (SCF-32).

A complex of phosphorous hydrogen with aluminum trichloride is prepared according to Example 1. To 16.9 g (0.1 mol) of the obtained complex, 8.5 g of a trifluorochloroethylene compound copolymer with vinylidene fluoride are added as a crumb. Remetanol and dried under vacuum to constant weight.

The content of P is 1.98 wt.%.

thirty

Claims (1)

Claim The method of obtaining phosphorus-containing polymers by processing halogen-containing the stock mixture is stirred in an atmosphere-35 polyolefin phosphorus derivative in Feert inert gas at 71) ° C. After 2 hours, a mixture of hydrochloric acid and ice is added to the reactor. The polymer is separated by filtration, washed with water, methyl alcohol and dried under vacuum to constant weight. The resulting polymer is insoluble in organic solvents. Content P 5.5% by weight 44.8 weight. ^ ' CB 14.4 wt.%. Example 6. Obtaining a phosphorus-containing polymer based on a copolymer of hexafluoropropylene with vinylidene fluoride (SCF-26). The complex of phosphorous hydrogen with aluminum trichloride is prepared according to Example 1. To 11.3 g (0.067 mol) of the obtained com / Tpex is added in the form of a crumb 2.44 g of a copolymer of hexafluorine in the presence of aluminum trichloride, characterized in that, in order to increase the degree of phosphorylation and reduce the duration 40 process, as a prod, one • phosphorus is used phosphorous hydrogen, which is pretreated with aluminum trichloride at OO-8O ° C, and the process is carried out in inertpropylene with vinylidene fluoride and 40 ml 55 "8; ? 459-464 (prototype). VNIIPI Order 1581/31 Circulation 512 Subscription 43 atmosphere.