SU1435582A1 - Method of producing grafted copolymers and grafted block-copolymers - Google Patents

Abstract

The invention relates to chemistry and the moquette to be used for the preparation of graft-modified copolymers of inorganic materials containing surface hydroxyl groups. The invention makes it possible to increase the grafting speed, increase the grafting rate and reduce the yield of side-by-side grafting of the homopolymer. This is achieved by treating solid inorganic material containing surface hydroxyl groups with phenyl-containing chloro- or alkoxy, or with acetoxysilane or their mixture in an amount of 0.07-0.45 wt.h. on 100 ma.ch. inorganic material, as well as additional processing first 0.05-120 wt.h. monochloride dimethyl ether per 100 parts m. inorganic material in the presence of a catalyst: Lewis islota, then 0.03-30 wt.h. N, N-disodium sodium per 100 ma.h. inorganic material, and sequential polymerization is carried out under the action of ultraviolet light. 2 tab. l (l have eaten sp 00 1c

Description

The invention relates to the field of production of modi-ny 1 by grafting inorganic materials containing surface and hydroxyl groups (silica gel, silochrome, aerosil, glass, etc.) in order to impart new properties to materials, to improve compatibility with the polymer matrix of fillers or dyes and for obtaining highly filled vinyl monomer based composite materials.

The use of grafted copolymers of grafted block copolymers in place makes it possible to combine the properties of homopolymers that are included in the grafted block copolymer molecule as its separate segments, to create materials combining regions with different polarities due to the same chemical nature of the chains. nature, having selective sorption and plasticization, the solubility of the dye, etc.

The aim of the invention is to increase the grafting rate, increase the grafting rate and decrease the yield of side-formed grafted homopolymer when preparing graft block copolymers.

Examples 1, 3.30 g (100 parts by weight of C-C-P silochrome are treated with a mixture of 0.33 g (10 parts by weight) of phenyltrichlorosilane and 30 ml of anhydrous benzene at room temperature for 2 hours, then silochro; washed with anhydrous benzene and chloroform. The resulting modified silochrome is placed in a flask equipped with a reflux condenser and mechanical stirrer, then a solution of 0.33 g (10 May monochloromethyl ether in 50 ml of chloroform and a catalyst is added - 0.04 g of tin tetrachloride The contents of the flask are heated for 2 hours with stirring, then prepared modified silochrome was washed with chloroform, alcohol, and acetone. The silochrome resin was obtained and placed in a flask equipped with a stirrer, then a solution of 0.165 g (5 May, h of K, H-diethyldithiocarbamate sodium in 40 MP acetone) was introduced: the contents of the flask were mixed into: 1 hour at room temperature, then wash the silochrome with acetone, Ba; and aiieTOHOM again, then dry it in vacuum until n

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worth of weight. 3.43 g of modified silochrome are obtained.

The resulting silochrome is divided into three equal parts, placed in ampoules, then 6 ml of methyl methacrylate are injected under vacuum conditions. Graft polymerization at 20 ° C is initiated with unfiltered UV light using a lamp 250 located at 10 cm from the ampoule. After the end of the experiment, the homopolymer is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess methanol. The resulting silochrome is dried in a vacuum to constant weight.

The dependence of the degree of grafting q on the duration of polymerization t of methyl methacrylate on the resulting silochrome, as well as the effect of the duration of polymerization t on the molecular weight M and the number of graft chains N of polymethyl methacrylate are given in Table. ,

When the methyl methacrylate is grafted on the unmodified silochrome under similar conditions, the degree of grafting is 0.

And pm. 2. p. 0.80 g (100 mash.) Of aerosil A-380, roll in a vacuum of 0.36 g (45 mash.) Of triphenylchlorosilane vapor for h, then aerosil is grafted hexane and methylene chloride. The resulting modified Aerosil is placed in a flask equipped with a reflux condenser and mechanical stirrer, then a solution of 0.96 g (120 parts by weight) of monochlorodimethyl ether in 50 ml of methylene chloride and a catalyst — 0.1 g of anhydrous zinc chloride are introduced into it. The contents of the flask are heated for 2 hours while peremegaivanii, after which the aerosil is rinsed with methylene chloride, alcohol and acetone. The resulting aerosil is placed in a flask equipped with a stirrer, then a solution of 0.24 g (30 May, part) S, sodium K-diethyldithiocarbamate in 50 ml of acetone is introduced. The contents of the flask were stirred for 1 hour at room temperature, then the aerosil was washed with acetone, water, and again with acetone and supta in vacuum to constant weight. Get 0.92 g of modified aerosil,

0.2 g of the obtained modified aerosil is placed in a vial, then 1A ml of methyl methacrylate and 2 ml of styrene are introduced under vacuum. Graft polymerization is initiated with unfiltered UV light, using a DRSh-250 lamp located at a distance of 10 cm from the ampoule as a light source. After the end of the experiment, the homopolymer is extracted with boiling benzene in a Socle apparatus for 30 hours, followed by separation of the homopolymer by introducing excess methanol. The resulting aerosil is dried under vacuum to constant weight. During the reaction time of 10 minutes, 0.297 g of grafted aerosil (degree of grafting 48.4%) are obtained. Homopolymers are O, 032 g (24.8% of the total amount of monomers which have been polymerized).

When grafting a mixture of methyl methacrylate and styrene on unmodified aerosil under similar conditions, the degree of grafting is 0.

PRI me R 3. 1.34 t (100 parts by weight of silica gel are treated with a mixture of 0.268 g (20 parts by weight) of diphenyldimethoxy silane, 0.16 g (12 parts by weight) of triphenylchlorosilane and 20 ml of hexane at 0 ° C for 4 hours, then the silica gel is washed with hexane and dioxane. The modified silica gel obtained is placed in a flask equipped with a reflux condenser and mechanical stirrer, then a solution of 1,072 g (80 parts by weight) monochloromethyl ether in 40 ml of dioxane and catalyst - 0.08 g of anhydrous aluminum chloride. The contents of the flask are heated for 1 hour, then the silica gel is washed with dioxane, water and alcohol, after which they are placed in a flask equipped with a stirrer, then a solution of 0.20 g (15 parts by weight) of sodium M, H-diethyldithiocarbamate in 30 ml of dimethylformamide is introduced thereto. The contents of the flask are stirred for 1 hour then, the silica gel is rinsed with methanol, water and enova with methanol, and then dried under vacuum to constant weight to obtain 1.432 g of modified silica gel.

The resulting silica gel is placed in a vial, then 10 ml of vinyl acetate are introduced under vacuum. Graft polymerization at 0 ° C is initiated with unfiltered UV light, using a DP11B250 lamp located 0m from the ampoule as a light source. After windows

An opmtl homopolymer is extruded with a KiniRptHM acetone in a Soxlet apparatus for 30 hours, followed by isolating the homopolymer by introducing an excess of hexagon. The resulting silica gel is supat in a vacuum to constant weight. During the reaction time of 5 minutes, 1.796 g of grafted silica gel (graft 25.4%) are obtained. Homopolymer receive 0,151 g (29.3% of the total number of polymerized monopomer

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When grafting vinyl acetate on unmodified silica gel under similar conditions, the graft level is 0.

PRI me R 4. 2.54 g (100 May, h) of the PMS-1600 macroporous glass is treated in vacuum with 0.0018 g (0.07 wt.h.) phenylmethyldiacetoxy-silane at 100 ° C for 1 h, then the glass is placed in a flask equipped with a reflux condenser and mechanical stirrer, after which a solution of 0.0013 g (0.05 parts by weight) of monochloride dimethyl ether in 30 ml of carbon disulfide containing 0.01 g of catalyst dichloride tin. The contents of the flask} are heated with stirring at 46 ° C for an hour, after which the glass is washed with - en.bach with carbon black, then with alcohol and treated with stirring with 0.0008 g (0.03 parts by weight) of H, K-diethyldithi thiocarbamate sodium in 20 ml of alcohol for 2 hours. The resulting glass is washed first with alcohol, then with water and again with alcohol, then dried under vacuum to constant weight. 2.542 g of modified glass are obtained.

The resulting glass is placed in an ampoule, then 10 ml of a 5% aqueous solution of metal-lysulfonate in methanol are introduced therein under argon. Graft polymerization is initiated with unfiltered ultraviolet light, using a DRSh-250 lamp located at a distance of 10 meters from the ampoules as a light source. After the end of the experiment, the homopolymer is extracted with boiling point methanol in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess diethyl ether. The resulting glass is dried under vacuum to constant weight. During the reaction time 30 min, 2.722 g of grafted are obtained.

glass (degree of grafting 7.1%). Homopolymers are obtained 0.009 g (4.8% of the total monomer which has polymerized).

: When carried out in similar conditions; metal sulphonate grafting on unmodified glass

: vaccinations equal C.

 PRI me R 5. 1.04 g (100 wt.h.) of silochrome C-120 is treated at room temperature with a solution of 0.156 g (15 parts by weight) of benzyltriethoxysilane in 20 ml of hexane for 2 hours, then the silochrome is washed hexanoi and chloro ™ form, after which it is placed in a flask equipped with a reflux condenser and mechanical stirrer. A flask is injected with a solution of 0.156 g (15 math. H) of monochloromethyl ether in 30 ml of chloroform, containing 0.08 g of anhydrous trichloro eluent jelly G a as a catapist; The contents of the flask are heated for 2 hours, then the silochrome is washed with chloroform and acetone, after which it is treated with a solution of 0.052 g (5 parts by weight) of sodium N, N-diethyl dithium dioI in 20 ml of acetone for 1 hour. The resulting modified silochrome washed with acetone, then with water and alcohol, and then dried in vacuum to constant weight. 1.10 g of modified chromium strength is obtained.

The resulting silochrome is placed in a vial, then 2 ml of a bin ;; ol and 8 ml of styrene are introduced under vacuum conditions. Wash polymerization at 80 ° C is initiated by light with a wavelength of D 365 nm, using a DRSh-250 lambles located at a distance of ør Å and 1Q cm from the ampoule as a light source. After the end of the experiment, the homopolymer is extracted with k-xssing β-benzene in the Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess 1: a of methanol. The resulting silochrome is dried under vacuum to constant weight. During the reaction time of 10 minutes, 1.574 g of grafted chromium (43.1% graft) is obtained. Homopolymers are obtained with 0.118 g (19.9% of the total amount of polymerized monomer).

When carried out in af analogous conditions of styrene grafting on unmodified force}: the degree of grafting is 0.

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PRI me R 6 (control, the amount of phenyl-containing silane is less than proposed). The experiment was carried out analogously to Example 4, using, as a modifier in the first stage, 0.0013 g (0.05 parts by weight) of phenylmethyldacetoxysilane. During the reaction time of 30 minutes, the degree of grafting of the metal sulfonate reaches 4%, and the homopolymer forms 3% of the total amount of the polymerized metal sulfonate.

PRI me R 7 (control, the amount of phenyl-containing silane is more than proposed). The experiment was carried out analogously to Example 2, using 0.40 g (50 parts by weight) of triphenylchlorosilane vapor. During the reaction time of 10 minutes, the degree of grafting of the mixture of methyl methacrylate and styrene reaches 48.4%, and the homopolymer forms 24.7% of the total amount of monomer polymerized.

Example 8 (control, the amount of monochloromethyl ether is less than proposed). The experiment was carried out analogously to Example 4, using 0.0010 g (0.04 parts by weight) of monochlorodimethyl ether. During the reaction time of 30 minutes, the degree of grafting of the metal sulfonate is 5.2%, and the homopolymer forms 4.1% of the increasing amount of polymerized monomer.

PRI me R 9 (control, the amount of monochlorodimethyl ether is greater than proposed). The experiment was carried out analogously to Example 2, using 1.04 g (130 parts by weight) of monochlorodimethyl ether. During the reaction time of 10 minutes, the degree of grafting of the mixture of methyl methacrylate and styrene reaches 48.2%, and the homopolymer forms 24.6% of the total amount of monomer polymerized.

Example 10 (control, treatment of inorganic material with mono-chlorodimethyl ether was carried out in the absence of a Lewis acid). The experiment was carried out analogously to Example 1, however, the treatment of silochrome with monochloride dimethyl ether was carried out in the absence of tetrachloride of tin. When the methyl methacrylate was grafted on the modified silochrome under similar conditions, the degree of grafting was equal to 0

Example II (control, without treatment of inorganic material N5N-sodium diethyldithiocarbamato).

The experiment was carried out analogously to Example 1, however, the modified silochrome was not treated with sodium K, H-diethyldithiocarbamate. When the methyl methacrylate is grafted on the resulting silochrome under similar conditions, the graft level for 30 minutes is equal to 0.2% and the homopolymer forms 96% of the total amount of monomer polymerized.

Example 12 (control, without processing inorganic material monochloromethyl ether). The test was carried out analogously to Example 1, but the additional treatment of the modified silochrome with monochloride dimethyl ether was not carried out. If methyl methacrylate is grafted under similar conditions on the obtained chromium, the degree of grafting in 30 minutes is 0.

Example 13 (control, without pretreatment of inorganic material — phenylsodone-containing silane). The test was carried out analogously to Example 1, however, the treatment of silochrome with phenyltrichlorosilane was not carried out. If methyl methacrylate is grafted under the same conditions on the obtained silochrome, the graft degree for 30 minutes is 0.

Example 14 (control, using phenyl-containing silane not containing chlorine, alkoxy or acetoxy groups). The test was carried out analogously to Example 1, however, tetraphenylsilane was used instead of phenyl trichlorosilane. When methyl methacrylate is grafted on the resulting silochrome under similar conditions, the degree of grafting is 0.

Example 15 (control, with a known silane). The experiment was carried out analogously to Example 1, however, instead of fefine-3-trichlorosilane, 10 ma.h. When methyl methacrylate is grafted under similar conditions on the obtained silochrome, the degree of grafting in 30 minutes reaches 32.4%, and the homopolymer forms 29.8% of the total amount of monomer polymerized.

Example 16 (control, using visible light). The tests were carried out analogously to example 1, however, graft polymerization was initiated with visible light, using a 250-watt quartz lamp as a light source. During the 30-minute relapse, the grafting rate of methyl methacrylate at the silochrome reaches 5.2%, and the homopolymer forms 34.2% of the total amount of monomer polymerized.

Example 17. Modification of silica gel with a mixture of diphenyldimethoxysilane-np and triphenyllorsilane, then monochlorodimethyl ether and I5K-diethyldithiocarbamate sodium is carried out according to the procedure described in Example 3. Modified silica gel is divided into three equal parts, placed in a quarto ampoule then, under conditions, vacuum is injected at 4 mp no. A. Primary polymerization is initiated with unfiltered light of a 1 kW UV lamp located 10 cm from the ampoule. After the end of the experiment, the homopolymer is extracted with boiling acetone in a Societte apparatus for 30 hours, followed by separation of the homopolymer by introducing excess methanol. The resulting silica gel is dried in vacuo to constant weight.

The dependence of the degree of vaccination on the duration of polymerization is given in table. 2

According to a known method, the degree of grafting of methyl methacrylate on silica gel is: 1 min - 22.2%, 5 min - 26.4%, 15 min - 38.5%, 30 min - 41.0%.

PRI me R 18. 3.30 g (100 mash of the C-120 silochrome are treated with a mixture of 0.33 g (10 wt.h.) of phenyltrichlorosilane and 30 ml of anhydrous benzene at room temperature for 2 hours , then the silochrome is washed with anhydrous benzene and chloroform.The resulting modified silochrome is placed in a flask equipped with a reflux condenser and mechanical stirrer, then a solution of 0.33 g (10 wt.h.) of monochlorodimethyl ether in 50 ml of chloroform and the catalyst is introduced into it 0.04 g of tin tetrachloride. The contents of the stake would be heated for 2 hours at 61 ° C. with stirring, then the resulting modified silochrome is washed with chloroform, alcohol, and acetone. The preparation is placed in a flask equipped with a stirrer, then a solution of 0.165 g (5 parts by weight) of N, N-sodium diethyldithiocarbonate in 40 ml of acetone is introduced therein.

for 1 h at room temperature, then the silochrome is washed with acetone, water and again with acetone, then dried in vacuum to constant weight. 3.43 g of modified silochrome are obtained. 1.14 g of the obtained silochrome is added into 1 ampoule, then under vacuum conditions 6 ml of methyl methacrylate are introduced. The graft polymerization at 20 ° C is initiated with unfiltered UV-Light, using the DP1P-250 lamp located at a distance of 10 cm from the ampoule as a light source. After the experiment is finished, the homopolymer is extracted with boiling acetone in a Soxhte apparatus for 30 hours, followed by separation homopolymer by the introduction of excess methanol. The resulting silochrome is dried under vacuum to constant weight. During the reaction time of 5 min, the grafting rate of methyl methacrylate reaches 8.0% (1.197 g of the grafted silochrome are obtained). The homopolymer forms - I with 20.1% of the total amount of methylmethacrylate that has been spilled or jo, 014 g,; Received grafted silochrome pome

Place in a vial, then 10 ml of styrene is injected under vacuum conditions. Graft polymerization at 20 ° C initial-. imit with unfiltered UV light as described above. After graduation

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Grafted homopolimetry methacrylate and homopolystyrene.

Example 19. 0.80 g (100 May, h. Aerosil A-360 is treated in vacuum O, 36 g (45 parts per hour) of trifenylchlorosilane vapor for 1 h, then aerosil is rinsed with hexane and methylene chloride The obtained modified aerosil is placed in a flask equipped with a reflux condenser and a mechanical stirrer, then a solution of 0.96 g (120 May, 4) of monochlorodimethyl ether in 50 ml of methylene chloride and the catalyst — 0, 1 g of anhydrous zinc chloride are introduced into it. The contents of the flask are heated for 2 hours with stirring, after which the aerosil is washed with chloride ylene, alcohol, and acetone. The resulting aerosil is placed in a flask equipped with a stirrer, a solution of 0.24 g (30 May, h) of T, K-diethyldithi- carbamate sodium in 50 ml of acetone is introduced therein. The contents of the flask are stirred for 1 at room temperature, then the aerosil is washed with acetone, water, and again with acetone and cyuiaT in vacuum to constant weight, to obtain 0.92 g of modified aerosil,

0.2 g of the obtained aerosil is placed in an ampoule, then 15 ml of methyl methacryl are introduced under vacuum conditions.

I experience homopolystyrene extracted with 35 Kita. Graft polymerization at

| With benzene in the Soxhlet apparatus for 30 hours, followed by its subsequent refinement by introducing an excess of methanol / The resulting grafted silochrome is dried in

20 ° C is initiated by unfiltered UV light according to the procedure described in Example 1. After the end of the first grafting stage, the homopolymer is extracted with a kiwakum to constant weight. Over time 40 acetone in Soxhlet's apparatus

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polymerization-styrene 60 minutes get 1,407 g of grafted silochrome. 0.050 g (19.2% of the total amount of polymerized styrene) is obtained from homopolystyrene.

Thus, with a total duration of polymerization. (5 + 60) 65 min, the total degree of grafting is 23.4%. The block structure of the grafted chains has been proven by selectively dissolving silochrome in hydrofluoric acid, followed by turbidimetric titration of the graft

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for JU h followed by separation of the homopolymer by the introduction of an excess of methanol. During the reaction time of 10 minutes, 0.308 g of grafted aerosil (degree of grafting 54.0%) are obtained. Homopolymethyl methacrylate gives 0.035 g (24.5% of the total amount of monomer polymerized). The grafted aerosil can be stored both in vacuum and in air for a long time without losing its initiating activity.

The resulting grafted aerosil polymer. The grafted chains contain 21% of the weight units of polymethyl methacrylate in the ampoule, then under vacuum conditions and 79% of the polystyrene units. Half-life is injected with 10 ml of vinyl acetate and the grafted silochrome is nearly 10 ml of acetone, the graft polymerization-pure grafted block copolymerization at 0 ° C is initiated by the procedure, rum containing trace amounts described in example 1. After finishing 20 With initiate unfiltered UV30

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for JU h followed by separation of the homopolymer by the introduction of an excess of methanol. During the reaction time of 10 minutes, 0.308 g of grafted aerosil (degree of grafting 54.0%) are obtained. Homopolymethyl methacrylate gives 0.035 g (24.5% of the total amount of monomer polymerized). The grafted aerosil can be stored both in vacuum and in air for a long time without losing its initiating activity.

The resulting grafted aerosil is placed in a vial, then 10 ml of vinyl acetate and 10 ml of acetone are injected under vacuum conditions, the graft polymerization at 0 ° C is initiated according to the procedure described in Example 1.

Neither experience the homopolymer is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, followed by isolation of the homopolivinylate etat by introducing an excess of hexane. The grafted aerosil is dried under vacuum to constant weight. During the polymerization of vinyl acetate in 10 minutes, 0.334 g of grafted aerosil is obtained, Homopolivinyl acetate is obtained in 0.008 g (23.5% of the total amount of polymerized vinyl acetate).

Thus, with a total polymerization time of 20 minutes, the total degree of grafting reaches 67.0%. ig time in air at room temperature The block structure of grafted chains was proved by selectively dissolving grafted aerosil in hydrofluoric acid followed by turbidimetric titration of graft polymer.20 The grafted aerosil obtained is a practically refined graft block copolymer containing trace amounts of grafted homopolymethyl methyrylate in the graft block copolymer 25, the polymer is 80.6 wt.%.

Example 20. 1.34 g (100 wt.h.) silica gel is treated with a mixture of 0.268 g (20 wt.h.) diphenyldimethoxysilane, 0.161 g (12 wt.h.) triphenylchlorosil-30 on and 20 ml of hexane at 0 ° C in for 4 h, then the silica gel is washed with hexane and dioxane. The resulting silica gel is placed in a flask equipped with a reflux condenser 25 and a mechanical blender, then a solution of 1.072 g (80 May, h) of monochloromethyl ether in 40 ml of dioxane and a catalyst — 0.08 g of anhydrous chloride aluminum. The contents of the flask are heated with dioxane, water, and alcohol, after which it is placed in a flask equipped with a blender containing a solution of 0.0101 g (15 parts by weight) of sodium N, N-diethyldithiocarbamate in 30 ml of dimethylformamide. The contents of the flask are transferred for 1 hour at 100 ° C, then the silica gel is rinsed with methanol, water and again with methanol, and then dried under vacuum to constant weight. 1.432 g of modified silica gel is obtained.

The resulting silica gel is placed in a vial, then 10 ml of vinyl acetate are introduced under vacuum. Grafting polymerization at 0 ° C is initiated with unfiltered UV light according to the procedure described in Example 1. After completion of the experiment, the homopolymer is extracted

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peruratu without losing its initiating activity.

The resulting grafted silica gel is placed in a vial, then 6 ml of butyl methacrylate and 4 ml of acetone are introduced under vacuum. Graft polymerization is initiated by light with a wavelength of nm. using the DRSh-250 lamp located at a distance of 10 cm from the ampoule as a light source. After the end of the experiment, the homopolymer is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess hexane. The grafted silica gel is maintained in a vacuum to constant weight. During the polymerization of butyl methacrylate for 5 minutes, 2.015 g of grafted silica gel is obtained. 0.056 g of homopolyb. Methyl methacrylate is obtained (20.4% of the total amount of butyl methacrylate which has been polymerized).

Thus, with a total polymerization time of 10 minutes, the total degree of grafting of the block copolymer reaches 40.7%.

In the obtained grafted silica gel, the grafted chains are chemically firmly bound to the surface of the inorganic material and are not separated as a result of hydrolysis with further long-term boiling of the grafted silica gel in water-containing acetone.

The block structure of the graft chains was proved by selectively dissolving the grafted silica gel in hydrofluoric acid, followed by turbidimetric titration of the graft polymer. The resulting grafted silica gel is a virtually pure graft block copolymer containing trace amounts of grafted grafts.

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boil with acetone in a Socles apparatus for 30 hours, followed by separation of the homopolymer by introducing an excess of hexane. The resulting silica gel. Suiat in a vacuum to constant weight. During the reaction time of 5 minutes, 1.796 g of grafted silica gel (graft 25.4%) are obtained. Q 0.151 g of homopolymer is obtained (29.3% of the total amount of polymerized vinyl acetate.

The grafted silica gel can be stored for a long time.

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peruratu without losing its initiating activity.

The resulting grafted silica gel is placed in a vial, then 6 ml of butyl methacrylate and 4 ml of acetone are introduced under vacuum. Graft polymerization is initiated by light with a wavelength of nm. using the DRSh-250 lamp located at a distance of 10 cm from the ampoule as a light source. After the end of the experiment, the homopolymer is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess hexane. The grafted silica gel is maintained in a vacuum to constant weight. During the polymerization of butyl methacrylate for 5 minutes, 2.015 g of grafted silica gel is obtained. 0.056 g of homopolyb. Methyl methacrylate is obtained (20.4% of the total amount of butyl methacrylate which has been polymerized).

Thus, with a total polymerization time of 10 minutes, the total degree of grafting of the block copolymer reaches 40.7%.

In the obtained grafted silica gel, the grafted chains are chemically firmly bound to the surface of the inorganic material and are not separated as a result of hydrolysis with further long-term boiling of the grafted silica gel in water-containing acetone.

The block structure of the graft chains was proved by selectively dissolving the grafted silica gel in hydrofluoric acid, followed by turbidimetric titration of the graft polymer. The resulting grafted silica gel is a virtually pure graft block copolymer containing trace amounts of grafted grains.

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13U35582

monopolivine acetic acid and homopolybutyl methacrylate. The content of polyvinyl acetate units obtained by the graft block polymer is 62.4% by weight. Example 21. 2.54 g (100 wt.h.) macroporous glass PMS-GbOO is processed in a vacuum of 0.0018 g (0.07 wt.h.) fnnilmetshtdiacetoksi- eilana for 1 h, then the glass is labeled in a flask equipped with a reflux condenser and a mechanical stirrer, after which a solution of 0.0013 g (0.05 wt.h.h) of monochlorodimethyl ether in 30 ml of carbon black containing 0.01 g of catalyst - two-chlorinated tin. The contents of the flask are heated with over- stirring at 46 ° C for 1 hour, after which the glass is washed first with carbon disulfide, then with alcohol and processed with stirring with a solution of 0.0008 g (0.03 cc) And, Sodium diethyldithiocarbamate in 20 ml of alcohol at 0 ° C for 2 hours. The resulting glass is washed first with alcohol, with water and again with alcohol, after which it is dried in a vacuum to a constant weight. 2.542 g of modified glass are obtained.

The resulting glass is placed in a vial, then 10 ml of butyl methacrylate are introduced under vacuum. Graft polymerization for 5 min when initiated by methodin

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The example described in Example 1, After: window-: The experience of butyl methacrylate is downloaded on a vacuum unit, and 6 ampoules of methyl methacrylate and 4 ml of acetone are condensed in an ampoule: under vacuum conditions. The graft polymerization at 20 ° C is initiated for 7 minutes by the procedure described in Example 1, then the acetone and the unpolymerized methyl methacrylate are downloaded in a vacuum unit, and in the ampoule it is condensed with 5 mp styrene and 5 ml benzene,

The third stage of vaccination poly40

PRI me R 22, 1.04 g (100 wt, h of silochrome C-120 is treated at room temperature with a solution of 0.156 g (15 May, h) of benzyltriethoxysilane in 20 ml of hexane for 2 h, then the silochrome is washed with hexane and chloroform j, after which it is placed in a flask equipped with a reflux condenser and mechanical stirrer. A solution of 0.156 g (15 May, including monochloromethyl ether in 30 ml of chloroform, containing 0.08 g of anhydrous trichloride as catalyst is introduced into the flask ferrous iron. Contained flasks are heated at 6l c for 2 h, then silochrome is washed with chloroform and a tone, then it for 1 h

merization is initiated for 10 min. 50 are bathed at 30 C with a solution of 0.052 g at 80 C with light e of wavelength L (May, h) K, K-diethyldithiocarbam-365 nm, using sodium source in 20 ml of acetone as a source. The obtained modified silochrome is washed with acetone, then with water and with alcohol, and then dried in vacuum to constant weight. Obtain 1.10 g of modified eilochrome. The resulting Cylochrome is placed in an ampoule, then under conditions of vacuum, 2 ml of light bennic is injected into a DRSh-250 lamp located 10 m from the ampoule. After the end of the experiment, the homopolymers are extracted with boiling benzene in the Soxhlet apparatus for 30 hours, followed by the separation of the homopolymers; - the introduction of an excess of methanol. Received0

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Dry the glass under vacuum to constant weight.

Thus, with a total polymerization time of 22 minutes, 3j287 g of grafted glass is obtained. The total degree of grafting is 29.3%). The total yield of homopolymers is 0.256 g (25.5% of the total amount of monomers polymerized),

The block structure of graft chains has been proven by selectively dissolving graft glass in hydrofluoric acid followed by turbidimetric titration of the graft polymer. The resulting graft glass is a substantially pure graft polymer with three grades containing trace amounts of graft homopolybutyl methacrylate, homopolimethyl methacrylate and homopolystyrene. The content of polybutyl methacrylate and polymethyl methacrylate units in the obtained twisted three-block copolymer is 14.5 and 31.3 wt.%,

When grafting butyl methacrylate, then methyl methacrylate and styrene on unmodified glass under similar conditions, the degree of grafting is O,

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PRI me R 22, 1.04 g (100 wt, h,) - silochrome C-120 is treated at room temperature with a solution of 0.156 g (15 May, h) of benzyltriethoxysilane in 20 ml of hexane for 2 h, then silochrome washed with hexane and chloroform j, after which it is placed in a flask equipped with a reflux condenser and mechanical stirrer. A flask was injected with a solution of 0.156 g (May 15, h) of monochloromethyl ether in 30 ml of chloroform, containing, as a catalyst, 0.08 g of anhydrous trichloric iron. The flasks were heated at 6 liters for 2 hours, then the silochrome was washed chloroform and acetone, then it for 1 h

shake at 30 ° C with a solution of 0.052 g (May, h,) K, sodium K-diethyldithiocarbamate in 20 ml of acetone. Received

The modified silochrome is washed with acetone, then with water and with alcohol, and then dried under vacuum to constant weight. Obtain 1.10 g of modified eilochrome. The resulting Silochrom is placed in a vial, then 2 ml of benzene and 8 ml of styrene are introduced under vacuum. The graft polymerization is initiated with light, with a wavelength of nm, using a DP1H-250 lamp located at a distance of 10 cm from the ampoule as a light source. After the end of the experiment, the homopolymer is extracted with boiling benzene in a Soxhlet apparatus for 30 hours, followed by release of chromium with a degree of grafting equal to 0.

molol.mera introduction of excess methanol. The resulting silochrome is dried under vacuum to constant weight. During the reaction time of 10 minutes, 1.574 g of grafted silochrome (graft degree 43.1%) are obtained. 0.118 g of homopolymer is obtained (19.9% of the total amount of polymerized styrene).

The grafted silochrome obtained can be stored for a long time in air without losing its initiating activity.

The grafted silochrome is placed in a vial, then 5 ml of vinyl acetate and 5 ml of benzene are introduced under argon atmosphere. Grafting polymerization is initiated at room temperature by unfiltered UV light according to the procedure described in Example 1. After completion of the experiment, the homopolymer is extracted with boiling benzene in a Societte apparatus for 30 hours, followed by separation of the homopolymer by introducing excess hexane. The grafted silochrome is dried under vacuum to constant weight. During the polymerization of vinyl acetate for 10 minutes, 1.923 g of grafted silochrome is obtained. Homopoliviniladate s 0.124 g (26.2% of the total amount).

25

ots

Analogously to Example 2, using 1.04 g (130 parts by weight) of monochlorodimethyl ether. With a total duration of polymerization of 20 minutes total

properties of polymerized vinyl acetate-40 ditch (27.7% of total colitis). Thus, with the total duration of the polymerized polymerization monomezyme 20 min sums,

mar the degree of grafting of the block copolymer. EXAMPLE 26 (control, the color is 74.8%. the amount of monochlorodimethyl ether

In the resulting material grafted 45 of the proposed). The experiment carried out polymer chains chemically firmly bound to the surface of the inorganic material and are not separated as a result of hydrolysis with further prolonged boiling of the material in water containing 50 degree of grafting of the soybenzene block copolymer. stands at 66.8%.

The block structure of the grafted chains is as follows: EXAMPLE 27 (control, quantitative by selective dilution of M, H-distildithiocarbamate and sodium grafted silochrome in hydrofluoric acid less than proposed). Pro-acid experience followed by turbidimetry 55 analogs to Example 4, using titration of a graft polymer. The grafted silochrome obtained is a virtually pure graft block-: copolymer containing trace amounts of 0.066 g (0.02 parts by weight), sodium K-diethyldithio carbamate. With a total duration of polymerization of 22 minutes, the total degree of grafting of block copolylicism of grafted homopolystyrene and homopolyvinyl acetate. The content of polystyrene units in the graft block copolymer obtained is 57.6% by weight.

When carried out under similar conditions, grafting of styrene, then vinyl acetic acid on an unmodified force.

0

Example 23 (control, the amount of phenyl-containing silane is less than the proposed one). The experiment was carried out analogously to Example 4, using, at the first stage of the modification, 0.0013 g

(0.05 wt.h.p.) phenylmethyldiacetoxy-silane. With a total polymerization time of 22 minutes, the total degree of grafting is 17.3%, and homopolymers form 28.4% of the total number of monomers that are polymerized.

Example 24 (control, the amount of phenyl-containing silane is more than proposed). The experiment was carried out analogously to Example 2, using 0.40 g (50 parts by weight) of triphenylchlorosilane vapor. With a total polymerization time of 20 minutes, the total graft ratio of the block copolymer is 67.1%. PRI me R 25 (control, the amount of monochloromethyl ether less than the proposed). The experiment was carried out analogously to example 4, using

c 0,0010 g (0.04 wt.h.) monochlorodimethyl ether. With a total polymerization time of 22 minutes, the total graft ratio of the block copolymer was 19.6%, and the homopolymeation was analogous to Example 2, using 1.04 g (130 parts by weight) of monochloromethyl ether. With a total duration of polymerization of 20 minutes total

 More than proposed). The experiment carried out the degree of grafting of the block copolymer was 66.8%.

 PRI me R 27 (control, the amount of M, H-distildithiocarbamate sodium is less than proposed). Experience similar to example 4, using

0.0006 g (0.02 wt.h.), sodium K-diethyldithiocarbamate. With a total polymerization time of 22 minutes, the total degree of grafting of the block copolymer is 18.7%, and the homopolymer is 27.27, of the total amount of monomers that have been polymerized.

PRI me R 28 (control., The number of N, N-flH3THJ flHTHOKap6aMaTa nat-J3HH more than proposed). The experiment was carried out analogously to example 2, using 0.28 g (35 May, h) of H, sodium K-diethyldihydro-carbamate. With a total polymerization duration of 20 minutes, the total degree of grafting of the block copolymer a is 66.9%,

EXAMPLE 29 (controlled, wounding () of an inorganic material with monoslordimethyl ether was discarded in a Lewis acid). The experiment was carried out analogously to Example 1, but the treatment of silochrome with monochlorodimethyl fiber was carried out in the absence of four-tin tin. When the inoculation of methyl methacrylate is carried out under illogical conditions, then of styrene on a semied silochrome, the degree of inoculation is 0.

PRI me R 30 (reference J without processing inorganic material, sodium M-diethyldithiocarbamate). Tried as in Example 1, but the modified silochrome is not treated with sodium K, H-diethyldithiocarbamam. When methyl methacrylate is grafted under the same conditions, then styrene on the resulting silo: the graft is 0.03%, in the second stage of polymerization, the styrene graft does not occur V. the resulting product is a methyl methacryle graft copolymer - jiaTa.

PRI me R 31 (control 5 without treating inorganic material with Nonochlorodimethyl 1.1 M ether). The experiment was carried out analogously to example 1, but one additional treatment of the modified 1 | silo eoma with mono.chlordomethine | ethyl ester was not carried out. When carried out under similar conditions of methyl methacrylate inoculation, then styrene on the resulting silochrome, piaBHa grafting ABOUT,

PRI me R 32 (control, without p | preliminary processing of inorganic material with phenyl-containing si-). The experiment was carried out analogously to the example, however, the treatment of silochrophenyltrichlorosilane was not carried out under the same grafting conditions of methyl methacrylate, then styrene on the resulting silochrome, the degree of grafting was 0.

Example 33 (control, using a phenyl-containing silane, not containing a chloro, alkoxy or acetoxy group), The experiment was carried out as in Example 1, however, instead of phenyltrichlorosilane, 10 m.ch. tftraphenylsilane. When methyl methacrylate is grafted under similar conditions, then styrene on the resulting silochrome, the graft ratio is O,

PRI me R 34 (control, with from CTi-uiM silane). The test was carried out analogously to Example 5; however, instead of, phenyltrichlorosilane is used 0 May, h. m tylvinyl dichlorosilane. When methyl methacrylate is grafted under similar conditions, then styrene on the resulting silochrome is grafted to 0.7%, and no graft block copolymer is formed.

Example 35 (control, using.-Irradiation). The test was carried out analogously to Example 1, but after modifying the silochrome, the resulting material was irradiated in the presence of methyl methacrylate with v-rays With a dose of 10 kGy. The graft level reaches 6%, and a graft block copolymer H is formed,

PREMI; p 36 (k), 1.20 g (100 May, h) of silochrome C-120 is treated with a mixture of 0.12 g (10 m.h. chloromethyldimethylchloroilane and 50 ml of anhydrous benzene at room temperature for 3 h, after which the silochrome was washed with anhydrous benzene, then with acetone and placed in a flask equipped with a mechanical stirrer. The flask was injected with a solution of Ojl8 g (15 parts by weight) of H5K-diethyldithiocarbamate sodium in 30 ml of acetone. The contents of the flask were mixed at room temperature for 3 hours, then the ethyl chloride is washed first with acetone, then with water and again with acetone, then dried in vacuo up to constant weight, get 1.286 g of modified silochrome.

The resulting silochrome is placed in a vial, then 10 ml of methyl methacrylate are introduced under vacuum conditions. Graft polymerization is initiated by the procedure 5 described in

Example 1 With a total polymerization time of 65 minutes, the grafting rate is 10.1%, and no graft block copolymer is formed.

P 37 and 37. 2.20 g (100 mash of the silochrome C-120 is treated with a solution of 0.44 t (20 mash) of methyl vinyl dichlorosilane in 20 ml of anhydrous benzene at 80 ° C for 25 hours, the silochrome is then washed with benzene and dried under vacuum to constant weight to obtain 2.29 g of the modified silochrome. The resulting silochrome is placed in an ampoule and irradiated under vacuum conditions at -196 ° C with t-rays of 10 kGy, then 10 ml of methyl methacrylate are introduced at room temperature.

The graft polymerization is carried out for 3 minutes, then the methyl methacrylate is downloaded in a vacuum unit and 10 ml of styrene are introduced into the vial under vacuum conditions. The graft polymerization is carried out at 20 ° C for 2 h, then the homopolymer is extracted with boiling benzene in a Soxhlet apparatus for 30 h followed by injection of the homopolymer by the introduction of excess methanol. The resulting silochrome is dried under vacuum to constant weight. Get 2,679 g of modified silochrome (the degree of vaccination of 17%).

The graft silochrome obtained along with the graft block polymer contains 27 wt.% Of the grafted homopolymethyl methacrylate formed in the first grafting stage.

EXAMPLE 38 (control, with IC using visible light). The tests are carried out as in Example 1, but the graft polymerization is initiated by visible light, using a 250 mW iodization-quartz lamp as a light source. from the ampoule. With a total polymerization time of 65 minutes, the total degree of grafting is 1.4%.

EXAMPLE 39 A modification of silica gel with a mixture of diphenyldimethoxysilane and triphenylchlorosilane, then monochloromethyl ether and H, H-diethyl dithiocarbamate sodium is carried out as described in Example 3. The modified silica gel is placed in a quartz ampoule, then vacuum conditions, 4 ml of MMA are introduced. At 355Й220

Vivech polcumerisation is initiated during 1 min with unfiltered light of a 1 kW UV lamp located 10 cm from 1 ampoule. After finishing the test, the homopolymer is extracted with boiling acetone in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by the introduction of excess methanol. Silica gel succulent under vacuum to constant weight. The degree of MMA vaccination reaches 27.2%, and the homopolymer forms 18.6% of the total amount of polymerization No.-1A. The grafted silica gel can be stored for a long time in air without losing its initiating activity,

20 To obtain a graft block copolymer, the resulting graft silica gel is placed in a quartz ampoule, then 5 ml of styrene are introduced under vacuum conditions. Graft polymerization at 20 ° C is initiated for 4 min with unfiltered light of a UV lamp mop1; 1 kW, located at a distance of 10 cm from the ampoule. After the end of the experiment, homopolystyrene is extruded with boiling benzene in a Soxhlet apparatus for 30 hours, followed by separation of the homopolymer by introducing excess methanol. The resulting silica gel is dried in vacuo to constant weight. Thus, with a total duration of polymerization (1 + 4) of 5 minutes, the total degree of grafting of the block copolymer reaches 41.4%. Homopolystyrene in the second stage

40 of the synthesis forms 22.7% of the total amount of styrene polymerized.

The block structure of grafted chains has been proven by selectively spreading the grafted silica gel in hydrofluoric acid followed by turbidimetric titration of the separated graft polymer. The grafted silica gel is practically

50 pure grafted block copolymer containing trace amounts of grafted homopolymethyl methacrylate and homopolystyrene. The content of PNMA units in the graft block copolymer 55 pe obtained is 66%.

Claims (1)

Invention Formula The method of obtaining graft copolymers and graft block copolymers the treatment of solid inorganic material containing surface hydroxyl groups with silane with the further interaction of the resulting inorganic inorganic material with vinyl and / or allyl monomers, the subsequent interaction of the grafted co-polymer with the vinyl monomer to the grafted (5 block copolymer, characterized in that, in order to increase the grafting rate, and also to increase the grafting rate and decrease the yield of the grafted homopolymer upon receipt of the grafted block 22 copolymers, phenylcontaining chlorine or alkoxy SI, or acetoxysnpane, or a mixture of them in an amount of 0, May, hours, May 100, hours, are used as silane. an inorganic material, the silane-modified inorganic material being additionally treated first with 0.05-120 May, h, monochloromethyl ether in the presence of Lewis acid, and then 0.03-30 May, h, sodium H5M-diethyldithiocarbamate for 100 May, h, inorganic material, and the grafting is carried out under the action of ultraviolet light. Table 1 table 2