SU725567A1 - Method of preparing copolymers - Google Patents

Abstract

1310134 Copolymerization process SUMITOMO CHEMICAL CO Ltd 17 July 1970 [22 July 1969 (2)] 34698/70 Headings C3G and C3P A vinyl or vinylidene aromatic monomer is copolymerized with a vinyl or vinylidene cyanide and/or an ester of a carboxylic acid containing a vinyl or vinylidene group in an aqueous medium containing as copolymerization regulator one or more of toluene, xylene, ethyl acetate, propyl acetate, butyl acetate and t-butanol. The copolymerization may be carried out in the presence of a conjugated diene polymer to give a graft polymer. Examples are given in which (a) acrylonitrile or methacrylonitrile is copolymerized with a mixture of mmethyl - alpha - methylstyrene and p - methylalpha-methylstyrene in an emulsion containing n-butyl acetate, the resulting copolymer being blended with a polybutadiene/acrylonitrile/ styrene graft polymer; (b) acrylonitrile or methacrylonitrile and the said mixture of styrenes are grafted on to polybutadiene in an emulsion containing n-butyl acetate and the resulting graft polymer is blended with the copolymer of acrylonitrile or methacrylonitrile, respectively, and the styrene mixture prepared as under (a); (c) acrylonitrile, methyl methacrylate and the said mixture of styrenes are copolymerized in an emulsion containing toluene; (d) the monomers as in (c) are grafted on to polybutadiene in an emulsion containing xylene; (e) methacrylonitrile and the said mixture of styrenes are grafted on to polybutadiene in an emulsion containing ethyl acetate and (f) acrylonitrile, styrene and the said mixture of styrenes are grafted on to polybutadiene in an emulsion containing xylene.

Description

II because this process pp when ne was wasp. implemented on an industrial scale. For these reasons, the temperature of the thermal warp of the sushi, which has high impact strength thermoplastic resins, is contained, their butadiene graft sonolimer remains below 120 ° C. Hence, the need for resin compositions with higher thermal stability is understood.

A known method for the preparation of copolymers by water-emulsification copolymerization a-dimethylstyrene a or its mixture with a diene polymer with (meth) acrylopitrate and / or vinylcarboxylic ester in the presence of an emulsifier, a polymerization initiator and a polymerization regulator-mercaptans 1.

The disadvantage of the method is that the polymerization process takes a relatively long time, and the copolymers are obtained with low indicators of physicomechanical properties.

This goal is achieved by the fact that in the process of obtaining copolymers by aqueous emulsion copolymerization of α-dimethylstyrene or its mixture with a diene polymer with (meth) acrylonptril and / or vinylcarboxylic ester in the presence of an emulsifier, a polymerization initiator and a polymerization regulator as a regulator Polymerization uses 0.001 to 50 parts by weight of a reactive mixture of a compound selected from the group consisting of toluene, xprol, ethyl acetate, propyl acetate, butyl acetate, and tertiary butanol.

Surprisingly, the copolymerization of high-polar monomers was found to be significantly accelerated in the presence of insignificant amounts of an appropriate organic solvent, such as for the monomers and for the polymers obtained from them, having a very low chain transfer constant and less polar than the original monomers. When using this solvent in the polymerization process, both the polymerization rate and the degree of polymerization increase. This opens up the possibility of commercially carrying out the copolymerization process of highly polar monomers. Thus, an aromatic, α-dimethylstyrene copolymer and an aromatic α-α-dimethylstyrene graft copolymer can be easily obtained, and, as a result, a heat-resistant resin composition can be prepared from a conjugated diene graft copolymer mixed with said copolymer.

Accordingly, the invention is based on the copolymerization method of high-polar monomers.

According to the proposed method, the copolymerization of a conjugated diene polymer with a homologue of vinyl benzene and with at least one of such compounds, such as vinyl cyanides and vinyl ethers of carboxylic acids, or copolymerization of homologue of vinyl biisol with at least one of such patterns, can be used with the same structure, as well as with the same patterns, they should be used with the same structure, as well as with the same structure, they should be used with the same structure. Carboxylic acids are carried out in an aqueous medium in the presence of an organic solvent. The latter is selected from among the following compounds; toluene, xylene, acetic acid ethyl ester, acetic acid propyl ester, acetic acid butyl ester, and tertiary butyl acid.

The difference between the proposed copolymerization is the use of these solvents, which play the role of a polymerization regulator. Pz of a huge number of organic solvents, only a variety of compounds are effective in terms of their task. The organic solvent is used in the process in an amount of from 0.01 to 50 parts (by weight) per 100 parts for all resin com pounds. Although any use of these organic solvents has a noticeable effect on copolymerization, some differences in efficiency, but apparently depend on the reaction system, reaction temperature, etc. For example, the efficiency of toluene is beneficial if the carboxylic acid ester is present in the reaction system and the course of polymerization is maintained below about 85 ° C. If the process temperature is above about 85 ° C, xylene is more efficient. If in the reaction system the main component is aromatic α-dimethylstyrene, then at a process temperature below about 75 ° C, it is advisable to use ethyl acetate as the polymerization regulator, and at a higher temperature, the best effect is obtained when using acetic acid butyl ester. In the case of the application of butyl ester of acetic acid or propyl ester of acetic acid, the effectiveness of their action is the same, whether the process will be at pyte temperature or more than 75 ° C. Tertiary butyl alcohol is effective up to 80 ° C as a polymerization regulator of the system, the main component of which is aromatic α-dimethylstyrene, but if there is vinyl carboxylic acid in the system, its effectiveness is much lower. In general, of the six solvents listed above, acetic acid butyl ester, acetic acid propyl ester, ethyl acetate and tertiary butanol are particularly preferred.

In the preparation of copolymers and graft copolymers like these, a-mercaptans can be successfully used as polymerization regulators. However, their use in the case of grading and graft copolymerization of a system whose component is an aromatic α-dimethylstyrene is undesirable because the resulting thermoplastic resin composition has poor physical properties.

Examples of the aromatic, α-dimethylstyrenes used in the inventive invention are l-methyl-a-methylstyrene, m-methyl-a-metpstyrene and o-methyl-a-methylstyrene. From the point of view of production, a mixture of l-methyl-a-mepstystyrene and its w-methyl-isomer is more preferred.

Styrene, o-viiiyltoluene, g-viiiyltoluene, l-vinyltoluene, α-methylstyrene, trimethylstyrene, etc. are used as vippliirovye bizpols that can be used together with aromatic α-dimethplystyrene.

Examples of viral cyanide are acryloyitrile and methacryloyitrile. Examples of the carboxylic acid vinyl ester are the lower alkrtlacrylate (for example, acrylic acid methyl ester, ethyl acrylate) and the lower alkyl methacrylate (for example, methyl methacrylate, ethyl methacrylate).

For example, polybutadiene, a copolymer of styrene with butamine, a copolymer of butamine with acrylonitrile, and the like are used as a conjugate polymer.

The copolymerization of these components is usually carried out by an emulsion polymerization or suspension polymerization method. Emulsion polymerization is particularly preferred if a higher molecular weight product is desired. The copolymerization process does not depend on the pH of the system, and the medium can be either alkaline or acidic. This is a significant advantage of the proposed method, since the process going in two or more stages does not require a stepwise control of the pH or its change in separate stages. An alkaline medium is generally preferred, since it is better emulsified, in which case it is not necessary to use highly efficient and expensive emulsifiers.

Thus, an aromatic α-dimethylstyrene soiolimer and an aromatic α-dnmethylstyrene graft soiolimer have been developed using the irim-saturated process. As a result, by mixing a graft copolymer, the main constituent elements of which are a conjugated diene polymer, a homologue of vinylbeizol, and at least one of such combinations, as vinyl cyanides and vinyl esters of carboxylic acids, with a co-polymer, the main constituent elements of which are homologues vinylbeisol and at least one of such compounds as vinyl cyanides and vinyl

carboxylic acid esters, characterized by considerable toughness and especially high heat resistance. Part of the graft copolymer and the copolymer, at least in one of them, the homologue of vinyl benzene is an aromatic, a-dimethylstyrene or a mixture of it with vinyl benzene. Therefore, it is necessary that

At the extreme, one of the copolymers — the graft-copolymer and the copolymer — had methylated styrene as the main constituent.

In the proposed method, the preference

It is given to such a graft-soiolimer, which contains 5-70% (oi weight) of the conjugated diene polymer and 95-30% (by weight) of co-polymerizable monomers, taken in different combinations. If the amount of conjugated Dondy polymer is less than 5% (by weight), the impact strength of the graft copolymer is insufficient. In case the amount of conjugated diene polymer exceeds 70% (by

graft soiolimer has excellent impact toughness, but its heat resistance is much worse.

All monomers and polymers used, and for example, conjugated diene polmer,

viilbenzene homologue, vinyl cyanide and carboxylic acid viiyl ester may be as described above.

Examples of copolymers are given below.

which can be used to compile thermoplastic resin commentations: acryloyitrile copolymer, m- and / or l-methyl-a-methylstyrene; a co-polymer of methyl acrylate, m- and / or l-methylstyrene; a copolymer of methacrylonitrile, m- and / or p-methyl-methylstyrene; copolymer of acrylonitrile, m- and / or l-methyl-methylstyrene and styrene; methyl methacrylate copolymer, mi / or l-methyl-a-methylstyrene; copolymer

acrylonitrile, methyl methacrylate, mn / or l-methyl-a-methylstyrene; a copolymer of methyl methacrylate, m- and / or l-methyl-amethylstyrene; copolymer of acrylonitrile, O-, m- and / or l-vinyltoluene, m- and / or parameter-a-methylstyrene; a copolymer of methacryloyitrile, O-, M-, and / or l-vinyltoluene, mi / or l-methyl-a-methylstyrene; copolymer of methacryloyitrile, m- and / or l-methyl-a-methylstyrene, styrene; a copolymer of metalacrylate, m- and / or l-methyl-a-methylstyrene, styrene; acrylonitrile and styrene co-polymer; a co-polymer of methacrylonitrile and styrene; acrylonitrile copolymer i.a-methylstyrene; a methacrylonitrile and amethylstyrene soiolimer; methyl acrylate and styrene soiolimer; copolymer of methyl methacrylate and styrene; a co-polymer of methacrylate and amethylstyrene, a copolymer of methyl methacrylate and a-methylstyrene; acrylonitrile copolymer, O-, m- and / or l-vinyltoluene and sti-.

rola; a copolymer of metacrplonitrile, o-, mi / nl p-vinyltoluene and styrene; etc.

Examples of graft soiolimers that can be used in the compositions are: polybutadiene graft copolymer, acrylonitrile, m- and / or l-methyl-a-methylstyrene; graft copolymer iolbutadiya. acrylonitrile, m- and / or p-methyl-a-methylstyrene and styrene; grap copolymer of polpbutadiene, methacryloylphenyl, m- and / or p-methyl-a-methylstyrene; graft copolymer of iolibutapepey, methyl acrylonirpla, lg / or ft-methyl-a-metpstyrene and styrene; graft-sonolymer of styrene-butadiene copolymer, acrylonitrile, m- and / or / g-methyl-a-methylstpropole; a graft-copolymer of styrene-butadiene soiolmer, acrylopitrile, I1-And / Or l-methyl-ss-methylstyrene and styrene; graft-copolymer of styrene-butadiene copolymer, methacrylonitrile, m- and / or l-methyl-a-methyl styrene a; graft-copolymer of styrene-butadiene sonolymer, methacrylonitrile, m- and / or l-methyl-a-methylstyrene and styrene; a graft copolymer of butadiene and acrylonitrile copolymer, acryloiitrile, m- and / or l-methyl-a-methylstyrene; graft-copolymer of butadiene-acryloyitrile soiolimer, methacryloyitrile, MI or p-methyl-a-methylstyrene; graft-copolymer of polybutadiene, methyl methacrylate, m- and / or l-methyl-a-methylstyrene; polybutadiene, acryloyitrile and styrene graft copolymer; graft copolymer of iolibutadiene, acrylonitrile and styrene; graft-soiolimer nolybutadiene, methacrylonitrile and styrene; graft soiolimer styrene-butadiene copolymer, acrylonitrile and styrene; graft-soiolimer of butadiene-acrylonitrile copolymer, acrylonitrile and styrene; graft-sonolymer polybutadiene, methyl acrylate and styrene; graft-soiolimer iolibutadiya, methyl methacrylate and styrene n, etc.

The main advantages of the invention are:

copolymerization of highly polimerized, highly polar monomers proceeds at a considerable rate and leads to the formation of a polymer with a high degree of polymerization;

copolymerization does not depend on the pH of the medium, so that it is possible to imbibe the dehydric emulsifier, and it is not necessary to adjust the pH at different stages of the process;

The previously complex process of graft copolymerization of a polymer with monomers prone to polymerization is now easily accomplished ....

The invention is illustrated in the irivedic examples below. In them, all parts and percentages are by weight. Physical parameters are determined by the following methods:

1) The intrinsic viscosity is determined in solution at 25 ° С, the solvent is chloroform, the method corresponds to the standard K 2283-1956.

, 2) Thermal warp temperature: (2-1) determined after annealing by heating to 105 ° C and holding at this temperature for 2 hours. Determination was carried out in accordance with the procedure described in ASTM (American Society for Testing Materials) D 648- 45T; (2-2) without annealing according to the method of ASTM D648-56.

3) Impact viscosity: (3-1) determination after annealing (heating to 105 ° C for 2 h) in accordance with the method of ASTM D256-54T. (3-2). Without annealing according to the method of AOST ASTM D256-54T.

4) Tensile strength: (4-1) is determined in accordance with the method of ASTM D638-52T; (4-2) determined in accordance with the method of ASTM D638-60T.

5) Lengthening - elongation at break.

6) Hardness - Rockwell hardness: (6-1) determined according to the method of .A.STM Д785-51; (6-2) determined in accordance with the method of ASTM D785-60T.

7) The fluidity is measured on a Coca nirnbore and is defined as the volume (ml) of resin flowing out of a nozzle with a diameter of 1 mm for 1 minute; (7-1) Iagrev up to 190 ° C, load- 60 kg; (7-2) heating up to 230 ° С, load - 60 kg.

8) The initial color is determined with the help of a color meter in accordance with the method of ASTM D1925-63T.

Example 1. 30 parts of acrnloiitrile, 70 parts of a mixture of w-methyl-a-methylstyrene and l-metpl-a-methylstyrene (in a weight ratio of 65: 35) (hereinafter referred to as dimethylated styrene) are charged to the reactor; 3 parts of sodium alkylnaphthalene sulfonate, 200 parts of water, 0.5 parts of potassium periprosulphate, 0.02 parts of seric acid, and 0.5 parts of acetic acid butyl ester as a polymerization regulator. The resulting mixture (pH 4) is subjected to emulsion polymerization at 75 ° C for 8 hours. The result is a resin emulsion (see example 1). Characteristic viscosity 0.87; Conversion 98%.

30 parts of acryloiitrile, 70 parts of dimethylated styrene, 3 parts of sodium alkylnaphthalene sulfonate, 200 parts of water, 0.5 parts of potassium trisulfate, 0.02 parts of seric acid and 0.2 parts of a mixed tertiary lycanthane are placed into the reactor. The resulting mixture (pH 4) is subjected to emulsion polymerization at

for 8 hours, while giving a resin emulsion (see comparative example 1).

The intrinsic viscosity is 0.60, the conversion rate is 98%.

A mixture of 50 parts of yolibutene latex (Trademark "FS-2004, produced by Firestone Co. Ltd), 15 parts of acryloitrile and 35 parts of styrene are subjected to emulsion polymerization, as a result of which a grafted rubber emulsion is obtained. 30 parts of the grafted rubber emulsion are mixed with 70 parts of the emulsin resin but Example No. 1 or Comparative Example No. 1. The mixture is salted out. Filter, wash with water and dry. The resulting powder was kneaded and rolled at 190 ° C for 10 minutes, with a final pressure of 100 kg / cm. From the prepared sheet cut plates of a certain size. They have been tested for specific physical properties.

The results are summarized in table. one.

Table 1

ten

prn 77 ° C for 12 hours. As a result, a resin emulsion is obtained (comparative index 2). Characteristic viscosity 0.45. Conversion 80%.

30 parts of the grafted rubber emulsion of example 1 are mixed with 70 parts of the resin emulsion of example 2 or comparative example 2. The prepared mixture is salted out, filtered, washed with water and dried. The resulting powder is then spun and rolled, molded under pressure. The prepared samples are subjected to tests to determine various physical properties.

The results are summarized in table. 2

table 2

20

25

Example 2. 30 parts of methacrylonitrile, 70 parts of dimethylnated styrene, 1 part of alkyl sodium naphthalate sulfonate, 3 parts, 2 parts of lauryl benzene sulfonate sodium, 250 parts of water are placed in the reactor. 0.5 parts of potassium persulfate, 0.02 parts of sulfuric acid and 0.5 parts of acetic acid butyl ester as a polymerization regulator. The prepared mixture (pH 4) is subjected to emulsion polymerization at 77 ° C for 8 hours, while giving a resin emulsion (hereinafter referred to as “example 2”), the characteristic viscosity is 0.78; Conversion 98%.

30 parts of methacrylonitrile, 70 parts of dimethyl uranyl styrene, 1 part of sodium alkyl naphthalene sulfonate, 2 parts of sodium lauryl benzene sulphonate, 250 parts of water, 0.5 parts of potassium perpyrosulfuric acid, 0.02 part of sulfuric acid and 0.2 parts of polymerization are placed in the reactor. tertiary mercaptan. The prepared mixture (pH 4) is subjected to emulsion polymerization

Example 3. A mixture of 50 parts of polybutadiene, 15 parts of acrylononthril and 35 parts of dimethyl styrene is subjected to emulsion polymerization. As a result of graft-co-complementing, graft-rubber is obtained. After adding 2 parts of alkylnaphthalene sulphonate, 2 parts of sodium lauryl benzene sulphonate, 350 parts of water, 0.5 parts of potassium nersulfate, 0.02 parts of sulfuric acid, and emulsifying with 0.5 parts of acetic acid butyl ester at pH 4 and

temperaure 80 ° C for 10 hours. An emulsion graft rubber was obtained (example 3). Characteristic viscosity 0.82. Conversion 98. In a similar technique, replacements are only

butyl acetate (0.5 parts) to mixed tertiary merkaitane (0.2 parts), which plays the role of regulator nolimerizac, get graft-rubber emulsion) (comparative example 3). In full

monomers enter, but graft copolymerization does not proceed.

The graft rubber emulsion of example 3 or comparative example 3 (30 parts) is mixed with the resin emulsion of example 1 (70 parts). The mixture is salted, filtered, poured, molded under pressure. Samples were exposed to the meanings of m. Certain physical characteristics are summarized in Table. 3

Table 3

Example 4. A mixture of 50 parts of polpbutadiene, 15 parts of methacrylopitrile, 35 parts of dimethylated styrene is saturated with emulsion nimerization. As a result of graft copolymerisation, graft rubber was obtained. After adding 2 parts of alkyl naphthalene sulphonate, 2 parts of sodium laurylbeisolsulfoiata, 350 parts of water, potassium persulphate (0.5 parts), 0.02 parts of seric acid to this mixture, and 0.5% of acetic acid butyl ester was used as polymerization regulator, an emulsion was added. iolnimerizapi. The mode of the process is 82 ° C, 10 hours. PH 4. A graft-rubber emulsion is obtained (example 4). Characteristic viscosity is 0.83. Conversion 98%.

Using a similar technique with the only change that, instead of acetic acid butyl ester (0.5 parts), a mixed tertiary mercaptan (0.2 parts) is taken as a polymerization regulator, a graft-rubber emulsion is prepared (Reference Example No. 4). Monomers enter into polymerization, but graft copolymerization is absent.

Table

The graft rubber emulsion of example 4 or comparative example 4 (30 parts) is mixed with the resin emulsion of example 2 (70 parts). The prepared mixture is evaporated, filtered, washed with water and dried. The resulting powder is kneaded and rolled, molded under pressure. On the prepared samples, measure different physical properties.

The results are summarized in table. four.

Example 5. 30 parts of acrylointryl, 70 parts of dimethyl styrene, 120 parts of water, 2 parts of sodium laurylbeisole sulfonate, 0.5 parts of peropyroserioxidium potassium were mixed into the reactor. The prepared mixture (pH 8) is subjected to emulsion full merisacin prp 70 ° C for 7 hours. The result is an emulsion resin. In parallel, copolymer iolibutadiene latex (trademark "FS-2004, and produced by Firestone Co. Ltd (50 parts), acrylonitrile (15 parts) and styrene (35 parts) are prepared with graft-emuls. The emulsion resin and graft emulsi are mixed, and the first in the amount of 70 parts (solid), and the second in the amount of 30 parts (solid). The prepared mixture is salted out, coagulated, splashed with water and dried. As a result, the powder is obtained.

In a nomep1 reactor, there are 30 parts of acrylonitrile, 70 parts of styrene, 120 parts of water, 2 parts of laurylbeisol sulfoate sodium, 0.1 part of sodium hydroxide and 0.5 parts of sulfuric acid. Cooked cream () is subjected to emulsion polymerization and 70 ° C for 8 hours, resulting in the receipt of a resin emulsion. Emu: 1c1o CMo.ibi is mixed with the above-described graft-emulsion, and it was taken in an amount of 70 parts per solid, and the second - 30 parts. The mixture is salted out, coagulated, washed with water and dried. As a result, a powder is obtained (hereinafter exemplified by “crawling example 5-1”).

30 parts of acryloiitrile, 70 parts of α-methyl methanol, 120 parts of water, 2 parts of sodium alkylnaphthalene sulfate, 0.001 parts of sulfuric acid, and 0.5 parts of a calcium sulfate are placed into the reactor. This mixture is subjected to emulsion polymerization and 70 ° C for 8 hours, resulting in a CMoyibi emulsion. The latter is mixed with graft-emulsion, above. The resin emulsion is taken in the amount of 70 parts (calculated on the solid mass), graft-emulsion - 30 parts. Prepared salt is salted, coagulated, eroded and dried. The result is a mink (see comparative example 5-2).

The powder is kneaded and rolled at 190 ° C for 10 minutes and molded under pressure at 190 ° C for 10 minutes, and the final molding pressure is 100 kg / cm. The resulting slab is cut into nlaetins of a certain size and is subjected to food testing to determine various physical properties.

The results are summarized in table. five.

13

EXAMPLE 6 Polybutadiene latex (50 parts), acrylonitrile (15 parts), dimethyl yarn styrene (35 parts), water (300 parts), sodium alkyl naphthalisulfurium sulfate (2 parts), potassium peroxylate acid (0.5 parts) and sulfuric acid (0.02 parts). The prepared mixture (pH 5) is polymerized at 70 ° C for 8 hours, resulting in a graft-emulsion containing a graft-polymer. The graft emulsion is mixed with the resin emulsion of Example 5, and the emulsions are calculated on the basis that the solid mass content of the emulsions is 30 parts and 70 parts corresponding. This mixture is salted out, coagulated, washed with water and dried. The result is a powder that is kneaded and rolled, and the mold is molded under pressure. Samples prepared from powder are tested for impact strength (3-2) - 16.7 kg / cm / cm (notched Izod), and the temperature of thermal distortion (2-2) is determined to be 103 ° C.

Example 7. Methacryloyitrile (30 parts), α-methylstyrene (70 parts), water (120 parts), sodium alkyl naphthalene sulfonate (2 parts), sulfuric acid (0.001 parts) and potassium persulfate (0.5 parts) are charged to the reactor. The prepared mixture is subjected to emulsion polymerization at 75 ° C for 8 hours, as a result of which a resin is obtained. It is mixed with the graft emulsion of example 6, and the emulsion is taken from the calculation, so that they are hard. the masses were in a mixture of 70 parts and 30 parts, respectively. The prepared mixture is salted out, coagulated, washed with water and dried. The resulting powder is kneaded and rolled, molded under pressure, and the physical properties of the samples are determined: temperature of thermal warping (2-2) 135 ° C; impact viscosity (3-2) 12.7 kg / cm / cm (in the 14th year with a break).

Example 8. In the reg.ktor download 30 parts of methacrylonitrile, 70 parts dimeti14

T a b l and ri and 5

molten styrene, 2 parts of sodium alklaphthalene sulfonate, 0.001 parts of sulfuric acid, and 0.5 parts of potassium tarsulfate. The mixture is subjected to emulsion polymerization at 70 ° C for 8 h, resulting in a gain emulsion resin. The resin emulsion is mixed with the graft emulsion of example b, and the emulsion is calculated on the basis that the solid masses contained in them are in a mixture of 70 parts and 30 parts correspondingly. The mixture is salted out. coagulate, washed with water and dried. The powder is kneaded and rolled, molded under pressure and samples are cut from the plate, which are fed to the test. Thermal warped temperature (2-2) 128 ° С. Impact viscosity (3–2) 12.0 kg / cm / cm (Izod with a flap).

Example 9. In a reactor, 55 parts of dimethyl yroinchene styrene, 35 parts of methyl methacrylate, 10 parts of acrylonitrile, 0.5 parts of potassium persulfate, 2.0 parts of

sodium acylnaphthalisulfonate, 2.0 parts sodium naurylbenzenesulfonate, 350 parts water, 0.02 parts sulfuric acid and 0.5 parts toluene (as a polymerization regulator). Prepared mixture

(RP 4) emulsion polymerized at 75 ° C for 6 hours. An emulsion resin is obtained (see Example 9-1).

Inherent viscosity 0.62. Conversion 98%.

By the same procedure as above, but using mixed tertiary mercaptan (0.5 parts) instead of toluene (0.5 parts) as a polymerization regulator, emulsion polymerization is carried out. The mode of polymerization is 75 ° C, 12 h. As a result, an emulsion resin is obtained (see comparative example 9-1).

Characteristic viscosity 0.59. Conversion 98%.

Polybutene latex (15 parts), :: - t-tlirovanny styrene (30 parts), methyl mgcrylate (45 parts) is placed in the reactor.

15

acrylonitrile (10 parts), water (240 parts), cumene hydroperoxide (0.5 parts), sodium laurylbenzenesulfonate (2 parts), dicrin (1.0 part), ferrous sulfate (0.01 part), sodium pyrophosphoric acid (0, 5 parts) and as a polymerization regulator xylene (0.3 parts). The mixture is subjected to emulsion polymerization at 87 ° C for 5 hours. A resin emulsion is obtained (see Example 9-2).

Coiveres 98%.

In a similar way, because of the use of the mixed greg-mercaptan (0.3 parts) as the polymerization regulator (0.3 parts) instead of xylene (0.3 parts), emulsion polymerization is carried out at 87 ° C for 12 hours. As a result, resin emulsion (see comparative example 9-2). Coiveres 96%.

A mixture of 50 parts of molibutadiya, 15 parts of methacrylonitrile and 35 parts of methylated styrene is subjected to emulsification of polymerization. In this case, a graft-copolymerization process takes place, leading to the formation of a graft-rubber. After adding Example 10. 15 parts of a yolpbutep latex, 50 parts of styrene, 240 parts of water, 0.5 parts of cumene hydroperoxide, 2.0 parts of laurylbeisol sulfoioate sodium, 1.0 part of dihydrate, 0.01 part of ferrous sulfate, 0.5 are placed in the reactor. parts of iatrophosphate iatrn and as a regulator of the polymer: ation of 0.3 parts of xylene. The mixture is subjected to emulsification polymerization at 87 ° C for 5 hours.

The result is a graft rubber emulsion.

Conversion 98%.

The graft rubber emulsion is salted out, coagulated, washed with water and dried. The resulting powder is kneaded and rolled, molded under pressure. The prepared samples are available for testing. The temperature of thermal warping (2-2) is impact strength (3-2) 18.2 kg / cm / cm (Izod with kink).

Example 11. Polybutadiene latex (FS-2204, product of Firestone 50 parts), acrylonntril (15 parts), aromatic d-dimethylstyrene (35 parts). tert-butanol (0.5 parts), water (350 parts),

sixteen

sodium alkylnaphthalene sulphonate (2 parts), sodium lauryl benzene sulphonate (2 parts), water (350 parts), potassium perioxyaryonic acid (0.5 parts), sulfuric acid (0.02 parts) and ethyl acetate (0, 5 parts) emulsion polymerization is continued as a polymerization regulator. Polymerization mode: pH 4; temperature 70 ° C; 9 h. As a result, a graft rubber is obtained (see irimer 9-3).

Characteristic viscosity is 0.83. Conversion 98%.

Similarly, but with the exception that mixed tertiary mercaptan (0.3 parts) instead of 0.5 part of ethyl acetate is used as a polymerization regulator, emulsion hardening is carried out at 70 ° C for 13 hours. Graft-rubber emulsion is obtained (see comparative example N ° 9-3). Conversion 94%.

The physical properties of the products corresponding to the various examples are summarized in table. 6

Table 6

the sodium derivative of alkylnaphthalene sulfoate (2 parts), sodium hydroxide (0.1 part) and pers) lfat kaln (0.5 tea) as a catalyst is subjected to emulsification and polymerization at a temperature of 70 ° C for 8 hours in order to obtain a "grafted emulsion."

The degree of contraction is 98%.

Separately acrylonitrile (30 parts), aromatic dimethylsgyrol (70 parts), sodium alkylidephthalisulfoate derivative (3 particular), water (100 parts), potassium persulfate (0.5 parts), sulfuric acid (0.02 parts) and treh-butanol (0.5 parts), undergo emulsion polymerization at a temperature of 75 ° C for 8 hours in order to obtain a "resin emulsion.

The degree of converted is 98%.

“The grafted emulsion (30 parts of solid material) and the resin emulsion (70 parts of solid material) are mixed. The displaced emulsion is coagulated, the product is washed with water and dried. The obtained powder is stirred, on rollers at a temperature of 190 ° C for 10 minutes, molded under pressure at 190 ° C with 11npj o :: o11 pressure levels of 100 kg / cm for 10 minutes, the resulting plate is diluted on samples of a certain size Example 12. Acrylonitrile ( 30 parts), aromatic α-dimethylstyrene (70 parts), iropyl acetate (0.5 parts), sodium proizvodioalkilnaphtalensulfonat

(3 parts), water (200 parts), potassium Iersulfate (0.5 parts) and sulfuric acid (0.02 parts) and subjected to emulsion polymerization at a temperature of 75 ° C for 8 hours to obtain a resin emulsion.

The conversion rate is 98%.

The "resin emulsion obtained in this way (30 parts of a solid substance) is mixed with an irivite emulsion in Example 1 (70 parts of a solid material). The resulting mixture is coagulated, the product is washed with water and dried. The resulting powder is mixed in a roll mill and then molded under pressure. The preparation plate is also used to measure various physical properties.

Example 13. Polybutadiene latex (“FS-2004, product of“ Firestone 50 parts), acrylonitrile (15 parts), aromatic α-dimethylstyrene (35 parts), toluene (50 parts), water (200 parts), disirrosive obietic acid ( 2 parts), sodium hydroxide (0.1 part) and potassium persulfate (0.5 parts, as a catalyst) and subjected to emulsion and polymerization at a temperature of 70 ° C for 8 hours. In addition, toluene was extracted in order to obtain a grafted emulsion.

Conversion rate is 96%.

The “grafted emulsion obtained as described above (40 parts of solid material) is mixed with a resin emulsion and reference 1 (60 parts solid material). The mixture was worked up as indicated in Example 1 and the уч urachaea were thus used to measure different physical properties.

The results are shown in Table. 7

Prnmer 14. Polybutadiene latex (“FS-2004, product from Firestone 50 parts), acrylonitrile (15 parts), aromatic a-dimethylstyrene (35 parts) toluene (0.01 part), water (200 parts), disirpionirovanie abletinic acid (2 parts), sodium hydroxide (0.1 parts) and potassium Iersulfate (0.5 parts as a catalyst) are subjected to emulsion polymerization and a temperature of 70 ° C for 10 hours to obtain a grafted emulsion. Coyversia degree 94%.

“The grafted emulsion (40 parts of solid material) is mixed with“ resin emulsion in Example 1 for syrups (60 parts of solid material). The mixture was worked up as indicated in Example 1, and the plate thus obtained was used to measure various physical properties.

The results are shown in Table. 7

Thus, the invention permits the acceleration of the process and the growth of co-polymers with good physicomechanical properties.

Claims (1)

Invention Formula The method of obtaining copolymers by a water-emulsion sonolmmerization of α-dimethylstyrene a or its mixture with a diene iolimer (with (meth) acryloi-trile and / or viylcarboxylic ester in the presence of an emulsifier, a polymerization initiator and a polymerization regulator, characterized in that, in order to accelerate the polymerization process and improve physicomechanical properties of copolymers, 0.01-50 parts of the weight of the reaction measure, which are used to measure various physical properties, are used as a regulator for the polymerization. The results are shown in Table. 7. T and l and II and 7 19YO CiViccti of a compound selected from sources, Information sources, consisting of toluene, xylene, ethyl acetate — taken into account at the examination ta, propyl acetate, butyl acetate, tertiary-1. U.S. Patent No. 3,629,211, Cl. 260-80.78, New butanol. Oublnk. 06/30/69 (nrotioty). TZbbb