SU1161520A1 - Method of obtaining graft copolymers - Google Patents

Abstract

A METHOD FOR OBTAINING PRIVATED COPOLYMERS by treating solid inorganic material containing surface hydro-. xyl groups, aminoorganoethox; Isilanum followed by graft polymerization of vinyl or allyl monomers or mixtures thereof in the presence of a polymerization initiator, which is described by grafting monomer, as an organoorganic synthysycholysylate synthesis, in order to increase the grafting rate and decrease the yield of the side homogenous homopolymer; , moreover, after treatment with if-aminopropyl (L-ethoxysilane 100 wt.h. inorganic material, it is additionally treated with O, 4-40 wt.h. lorangidrida trichloroacetic acid, and as the polymerization initiator used tetrakis (triethyl phosphite) nickel .and / or tetrakis (triphenyl phosphite) nickel in an amount of 1 10 - .1 1 mol to 10 mol / L.

Description

The invention relates to the preparation of grafted modified inorganic materials containing surface hydroxyl groups (Silica gel, Aerosil, Perlite, glass, etc.) to impart new properties to the materials, to improve the compatibility with the polymer matrix of fillers or dyes and to obtain strongly filled composites based on vinyl or allyl monomers or mixtures thereof.

A known method for producing graft copolymers by pre-irradiating an inorganic material with ionizing radiation followed by the introduction of a mixture of monomer with orthophosphoric acid U.

However, this method can only be used for the length of mTetracrylate or allyl monomers or their mixtures; moreover, it is characterized by a low grafting rate.

A known method for producing graft copolymers by pretreatment of inorganic materials is an organosilicon compound of the general formula

. )

where X is a halogen atom;

Y is a direct chemical bond or a bivalent organic radical, containing from 1 to 7. atoms of the molecule

 - a halogen atom or an alkoxy radical containing from 1 to 6 carbon atoms, followed by the graft polymerization of vinyl monomers in the presence of carbonyls or aryl cyanides of transition metals, or carbonylphosphine complexes nick "l and iron 23."

The disadvantages of this method are the low grafting rate of 0.05-4.1% per hour, as well as the formation of a large amount of a homopolymer of graftable monomer along with the polymer grafted.

There is also known a method for producing graft copolymers by pretreatment of an inorganic material (methyldichlorophen) with trichloroacetic acid propyl ester followed by graft polymerization in the presence of transition metal carbonyls under the action of visible light DJ. However, this method can only be used for grafting on inorganic materials that are transparent in the visible light region; moreover, it is characterized by a relatively low graft rate and the formation of a large amount of homopolymer of graftable monomer along with the grafted polymer.

The closest to the invention to the technical essence and the achieved result is a method of obtaining graft copolymers by treating solid inorganic material containing surface hydroxyl groups with an amino organo-ethoxysilane, followed by grafting polymerization of vinyl or allyl monomers or their mixture in the presence of a polymerization initiator. Solid inorganic materials are treated with y - (dimethylaminopropyp) methyldiethoxysilane in the temperature range from minus 20 to 400 ° C, followed by graft polymerization of vinyl or allylic monomers or their mixtures in the presence of aromatic ketones under the action of light with a wavelength of from 350 to 500 nm in the temperature range from minus 20 to (4.

However, the known method can only be used for grafting on inorganic materials that are transparent in the wavelength range of 350-500 nm. Moreover, it is characterized by a relatively low grafting rate and the formation of a large amount of homopolymer of graftable monomer along with the grafted polymer.

The purpose of the invention is to increase the grafting rate and decrease the yield of the side-formed homopolymer of the graftable monomer.

The goal is achieved by the fact that according to the method of obtaining graft copolymers by treating solid inorganic material containing surface hydroxyl groups with an amino organo-ethoxysilane, followed by grafting polymerization of vinyl or allyl monomers or their mixture in the presence of a polymerization initiator, it is applied as an aminoproplite ethotect et allyl monopropyltriorite ethocylite, ethomectylite et alisilane ethoxylate, ethotectit, etc. moreover, after treatment with α-aminopropyltriethoxy and Lane 100 wt.h. inorganic material it is additionally processed 0.4-40 mach. trichloroacetic acid chloride, and tetrakis (triethylphosphite) nickel and / or tetrakis (trifenstphosphite) nickel are used as the polymerization initiator, in an amount of 1 10 mol / l. Inorganic materials with 5-aminopropyltriethoxysilane can be treated in a wide range of temperatures, for example, from 0 to 250 ° C, however, to avoid energy losses, the process is carried out at room temperature, in -Aminopropyltriethoxysilane is introduced in the form of pairs or its solutions are used in organic solvent x. Processing of inorganic materials modified with f -amnopropyltriethoxysilane with trichloroacetic acid chloride can be carried out in a wide range of temperatures, for example, from 0 to 150 ° C, however, to avoid energy losses, the process is carried out at room temperature. During the graft polymerization, the concentration of tetrakis (three ethnophosphite) nickel or tetrakis (triphenylphosphite) nickel or their mixture in the reaction system varies widely, for example from I 10 to mol / L. Grafting of vinyl or allyl monomers or their mixtures is carried out in a wide range of temperatures, for example, from 0 ° C to 80 ° C. Both pure monomer and its mixture with an organic solvent are used. The graft polymerization reaction to solid inorganic materials pretreated with U-aminopropyltriethoxysilane, then with trichloroacetic acid chloride, initiates the resulting organic radicals chemically and hydrolytically bound to the surface of the inorganic material and, in the case of vaccination, you can apply one to one side. the polymer is bound to the surface by an unstable Si-0-C bond. 204 Example 1.2, South (100 mAh. CH; silochrome C-120 is treated at room temperature with a mixture of 0.50 g of jf-aminopropyltriethoxysilane and 50 ml of anhydrous benzene for 2 hours, then the silochrome is washed with benzene and dried in vacuum to constant weight 2.35 g of modified silochrome is obtained. The obtained silochrome is treated with a mixture of O, 315 g (15 ma.ch) of trichloroacetic acid chloride and 20 ml of anhydrous dimethylformamide at room temperature for 1 h, then the silochrome is washed with anhydrous dioxane and dried in Vacuum e. to constant weight. 2.25 g of modified eilochrome. The eilochrome obtained is placed in a vial, then 10 ml of methyl methacrylate containing tetrakis (triphenylphosphite), nickel in mol / l is introduced into it. Graft polymerization is carried out at 20 ° C. After the experiment is completed, the homopolymer is extracted boiling acetone in the Soxhlet apparatus for 30 h, followed by homopolymer separation by introducing an excess of methanol. The resulting silochrome suatat in vacuum to constant weight. Reaction time 30 min. Get 3,421 g grafted silochrome (the degree of vaccination of 41.1%). 0.052 g of homopolymer is obtained (5% of the total amount of monomer polymerized). In the resulting material, grafted EPIs are chemically firmly bound to the surface of the material and are not separated by hydrolysis with further prolonged boiling of the material in water-containing acetone. When the methyl methacrylate graft polymerization is carried out in similar words on an unmodified silochrome, the degree of grafting of Rav 0. Example 2. 1.25 g (100 ma.ch) of round obsidian process 0.01 g of α-aminopropyltriethoxysilane vapor at 250 C for 1 h in an acum then the obsidian is dried in a vacuum of constant weight. 1.255 g of modified obsidian are obtained. The obtained obsidian is treated in an acum of 0.005 g (0.4 parts by weight) of trichloroacetic acid lorane anhydride vapor at 50 ° C for 2 h, then the mixture is washed with anhydrous -1m dioxane and dried under vacuum to constant weight. 1.257 g of modified obsidian are obtained. Obtained obay dian is placed in a vial. Then, in an argon atmosphere, 10 ml of a 5% aqueous solution of metal sulfonate in methanol containing tetrakis (triethylphosphite) nickel in a concentration of 1 ± 10 mol l were introduced into a vial. Grafting polymerization is carried out at 80 ° C. After the end of the experiment, the homopolymer is extracted with boiling methanol in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess diethyl ether. The obtained obsidian is dried in vacuo to. constant weight. Reaction time 30 min. Obtain 1.312 g of grafted obsidian (degree of grafting 4.4%). 0.0004 g of homopolymer is obtained (0.7% of the total amount of the monomer used). When the grafting polymerization of allyl sulfonate on unmodified hammer obsidian was carried out under the same conditions, the graft ratio is 0. Example 3. 1.45 g (Eubmas. Silica gel is treated at room temperature with a mixture of 0.4 g of y-aminopropyltriethoxysilane and 20 m of anhydrous hexane for 3 h , then the silica gel is washed with hexano and dried under vacuum to constant weight to obtain 1.914 g of modified silica gel. The resulting silica gel is taken up in a mixture of 0.325 g (26. mas.) of trichloroacetic acid chloride and 20 ml of anhydrous hexane at room temperature for 1 hour, then the silica gel is washed with anhydrous dioxane and dried under vacuum to constant weight. 2.121 g of modified silica gel is obtained. The resulting silica gel is placed in an ampoule, then Yuli styrene containing tetrakis ( triethylphosphite) nickel in mol / l.The graft polymerization is carried out at 35 ° C. After the test, the homopolymer is extracted with boiling benzene in a Secant apparatus for 30 hours, followed by separation of the homopolymer by introducing an excess of methanol. The resulting silica gel is suiat in vacuo to postdone 1 eu. Reaction time 10 min. Receive 2.935 g of grafted silica gel, grafting rate of 38.4%). 040 g of homopolymer is obtained (4.7% of the total amount of the polymerized onomer). When the styrene was grafted on an unmodified snacikel in similar words, the degree of rivivka is 0. Example 4. 0.80 g (100 mas. Hours) of aerosil are treated with a mixture of 0.50 g of U-aminopropyltriethoxysilane and 50 ml of anhydrous toluene at 12 hours, Aerosil is then washed with toluene and dried under vacuum to constant weight. 0.969 g of modified aerosil is obtained. The obtained aerosil is treated with a mixture of 0.32 g (40 parts by weight) of trichloroacetic acid chloride and 50 ml of anhydrous toluene for 12 hours, then the aerosil is washed with anhydrous dioxane and dried in vacuo to constant weight. 1.182 g of modified aerosil are obtained. The resulting aerosil is placed in a vial, then a mixture of 40 ml of methyl methacrylate, 5 ml of benzene and 5 ml of vinyl acetate, containing tetrakis (triphenylphosphite) nickel at a concentration of 1-10 mol / l and tetrakis (triethyl phosphite) nickel at a concentration of 0.5% mol / l. The graft polymerization is carried out at 80 ° C. After the end of the experiment, the homopolymer is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, then the aerosil is dried in vacuum to constant weight. The homopolymer is isolated by introducing an excess of hexane. Reaction time 10 min. Get 4,150 g of grafted aerosil (degree of grafting 251.1%). 0.173 g of homopolymer is obtained (5.5% of the total amount of monomer polymerized). When the mixture of methyl methacrylate and vinyl acetate was grafted on unmodified aerosil under similar conditions, the degree of grafting is 0. Example 5 (control, the amount of trichloroacetic acid chloride is more than proposed). 0.80 g (100 wt.h.) of aeroeil is treated with a mixture of 0.50 g in α-aminopropl triethoxysilane and 50 ml without 7.

toluene for 12 hours, then aerosil is washed with toluene and dried in vacuo to constant weight. 0.969 g of modified aerosil is obtained. The obtained aerosil is treated with a mixture of 0.40 g (50 wt.%) Trichloroacetic acid chloride and 50 ml of anhydrous toluene for 24 hours, then aerosil is rinsed with anhydrous toluene, then with anhydrous dioxane and dried in a vacuum to constant weight ,. 1.182 g of modified aerosil are obtained. The graft polymerization of a mixture of methyl methacrylate and vinyl acetate is carried out according to the procedure described in Example 4. During the reaction time of 10 minutes, the grafting rate reaches 250.3%. 5.6% of the homopolymer is obtained from the total amount of monomer polymerized.

PRI me R 6 (control, the amount of trichloroacetic acid chloride is less than proposed).

 g (100 parts by weight) ground obsidian is treated in vacuum with 0.01 g of v-aminopropyltriethoxysilane vapor at 25 ° C for 1 hour. Then the obsidian is dried in vacuum to constant weight. 1.255 g of modified obsidian are obtained. The obtained obsidian is treated in vacuum with 0.0025 g (0.2 parts by weight) of trichloroacetic acid chloride vapor at 150 ° C for 2 hours, then the obsidian is washed with anhydrous dioxane and dried in vacuum to constant weight. 1.257 g of modified obsidian are obtained. The grafting polymerization of metal sulfonate was carried out according to the procedure described in Example 2. During the reaction time of 30 minutes, the grafting rate reaches 3.1%. 0.6% of the homopolymer is obtained from the total amount of monomer polymerized.

g

PRI M E R 7 (control, without additional processing of inorganic material Y-aminoproyltriethoxysilane).

1.05 g (100 parts by weight) of silica gel is treated with a mixture of 0.273 g (26 parts by weight) of trichloroacetic acid chloride and 20 ml of anhydrous hekean at room temperature for 5 hours, then the silica gel is washed with anhydrous dioxane and dried in vacuo to a constant weight.

208

When carrying out the grafting polymerization of esterol for 60 minutes on the resulting silica gel according to the method described in Example 3, the graft degree is 0.

Example 8, (control, without additional processing of inorganic material with trichloroquenoic acid chloride).

1.40 g (100 wt.h.) of elochrome C-120 is treated at room temperature with a mixture of 0.30 g of α-aminopropyltriethoxysilane and 50 ml of anhydrous benzene for 2 hours, then silochrome is washed with benzene and dried in vacuum to constant weight. 1.49 g of modified eilochrome are obtained. When conducting graft polymerization of metstmethacrylate on the obtained silochrome for 30 min according to the procedure described in Example 1, the degree of grafting is 0.

Example 9 (control, with a known initiator).

The treatment of ground obsidian with y-aminopropyltriethoxysilane, then trichloruke-chenyl chloride, was performed by the procedure described in Example 2. 1.50 g of modified obsidian was placed in amine. 10 ml of a 5% solution of metal sulfonate in methanol containing benzophenone at a concentration of 6-10 mol / l are introduced into the pool, then under vacuum conditions. Grafting polymerization at 20 ° C is initiated with visible light, using a 100 W halogen lamp located 10 cm from the ampoule as the light source. When carrying out the graft polymerization of metal sulfonate on modified obsidian for 30 minutes, the degree of grafting is 0.

Example 10 (control, with a known initiator).

The milled obsidian is treated with γ-aminopropyltriethoxysilane, then trichloroacetic acid chloride is carried out according to the procedure described in Example 2. 1.34 g of the obtained obsidian is placed in a vial, then 10 ml of methyl methacrylate are injected under vacuum conditions, containing carbon monoxide manganese in Concentrations 4.2-10 Mole / l. Primary polymerization is carried out at 20s and inunuiUpyioT 9 with light with a wavelength of 436 nm, using a 100 W halo lamp as a light source located at a distance of 10 cm from the ampoule. During the graft polymerization for 30 min, the degree of grafting It is 0.1% and forms 14% of the homopolymer of the total amount of polarized monomer. Example 11 (control, with known initiator) Treatment of ground obsidian with aminopropyltriethoxysilane, then trichloroacetic acid chloranhydride was carried out as described in Example 2. 1.42 g of the obtained modified obsidian was placed in a vial, then 10 ml were injected under vacuum conditions. methyl methacrylate containing 1% azodiisobutyric acid dinitrile. The grafting gamle polymerization is carried out at 70 ° C. During the reaction time of 30 minutes, the grafting rate reaches 0.03%, and 97% of the homopolymer is formed based on the total amount of polymerized monomer. Example 12 (control prototype). 1.40 g of silochrome C-120 is treated at room temperature with a mixture of 0.40 g of Jf - (di-methylaminopropyl) methyldiethoxysilane and 50 ml of anhydrous benzene at room temperature for 2 hours. Then the silochrome is washed with benzene and dried in vacuum to constant this weight. Get 1,312 modified silochrome. The resulting silochrome is placed in an ampoule, then under vacuum conditions, 10 ml of a solution of fluorenone in methyl methacrylate in a mol / l concentration is introduced there. The grafting field at 20 ° C is initiated by light with a wavelength of 9,405 nm, using a 100 W halogen lamp as a light source located 10 cm from the ampoule. After the end of the experiment, the homopoly Mepi is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, followed by the separation of the homopolymer by the introduction of excess methanol. The grafted silochrome is dried under vacuum to constant weight. Reaction time 30 min. Get 1,604 g grafted silochrome (degree of vaccination of 6.1%). 0.016 g of homopolymer is obtained (l 4.8% of the total amount of polymerized monomer). Example 13: (control, prototype). 1.00 g of ground obsidian is treated in vacuo with 0.01 g of vapors of - (dimethylaminopropyl) methyldiethoxysilane at 250 ° C for 1 h, then obsidian cyniaT in vacuum to constant weight. 1.003 g of modified obsidian is obtained. The obtained obsidian is placed in a vial, and then under vacuum conditions 10 ml of a 5% aqueous solution of metal sulfonate in methanol containing benzophenone at a concentration of 610 mol / l are introduced into it. Grafting polymerization at 20 ° C is initiated with visible light, using a 100 W halogen lamp located 10 cm from the ampoule as the light source. After the end of the experiment, the homopolymer is extracted with boiling methanol in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by the introduction of excess diethyl ether. The obtained obsidian is dried under vacuum to constant weight. The reaction time of 30 minutes get 1,0032 g grafted obsidian (grafting degree of 0.02%). This gives 0.00002 g of homopoly gg g - a measure (9% of the total amount of monomer that has been polymerized). Thus, it is clear from the examples given that when graft polymerization is carried out on solid inorganic material treated only with α-aminopropyltriethoxysilane, in the presence of tetrakis (triphenylphosphite) nickel as a polymerization initiator no graft polymer is formed. The graft copolymer is also not formed when graft polymerization is carried out on an inorganic material treated with trichloroacetic acid chloride only. When the graft polymerization is carried out on an inorganic material pretreated with α-aminopropyltriethoxysilane, then trichloroacetic acid chloride in the presence of benzophenone or dinitrile of azodiisobutyric acid, the graft copolymer also does not form as a polymerization initiator. In addition, when using a transition metal carbonyl as an initiator during grafting

P

Polymerization on solid inorganic material, which is opaque in the visible light region (obsidian), pretreated with jf-aminopropyltriethoxysilane, then trichloroacetic acid chloride, is practically impossible to inoculate the vinyl monomer. Additional processing 100 mach. inorganic material after its treatment with Y-aminopropyltriethoxysilane less than 0.4 wt.h. trichloroacetic acid chloride leads to a decrease in the rate of grafting, while additional processing 100 wt.h. inorganic material more than 40 mah. trichloroacetic acid chloride does not lead to a further increase in the grafting rate and a decrease in the yield of the side-formed homopolymer of the graftable monomer, and it is also not unnecessarily accompanied by an unproductive consumption of tri61520 chloride .12

chloroacetic acid at the stage of preprocessing, swelling of inorganic material.

Thus, the proposed method of obtaining graft copolymers extends the scope of application of the known method, extending it to inorganic materials that are opaque in the visible light region,

10 increases by 6.7 times the grafting rate compared to the prototype and by 3.3 times compared to the base object, as well as by 3 times the output of the graft monomer polymer formed by grains 15 compared to the prototype while maintaining a strong chemical bond between the grafted polymer and inorganic material. In addition, the proposed method simplifies the preparation of graft copolymers, since it does not require the use of irradiation with light. And it is applicable to any inorganic, materials containing surface hydroxyl groups.

Claims (1)

METHOD FOR PRODUCING GRAVED COPOLYMERS by treating solid inorganic material containing surface hydro, xyl groups with amino organoethoxysilane followed by grafting of vinyl or allyl monomers or a mixture thereof in the presence of a polymerization initiator, characterized in that, in order to increase the grafting rate and decrease the yield the forming homopolymer of the graftable monomer, χ-aminopropyltriethoxysipane is used as aminoorganoethoxysilane, and after edema of U-aminopropyltriethoxysilane 100 m.h. inorganic material is additionally treated with O, 4-40 m.h. trichloroacetic acid chloride,, and nickel tetrakis (triethylphosphite) and / or nickel tetrakis (triphenylphosphite) are used as the polymerization initiator in the amount of: 1 '10 “ ^t - .1 · 10 * mol / l. <"*> - S.U and" 1161520 .1161520