JPS63268712A - Production of copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer having excellent compatibility with various materials and good heat-resistance, strength and chemical resistance, by copolymerizing an unsaturated carboxylic acid monomer, etc., an aromatic vinyl monomer, etc. and a comonomer in the presence or absence of a thermoplastic resin, etc., under specific condition. CONSTITUTION:The objective copolymer can be produced by copolymerizing (A) one or more monomers selected from maleimide monomer, unsaturated carboxylic acid monomer, etc., (B) one or more monomers selected from (i) aromatic vinyl monomer, (ii) unsaturated nitrile monomer and (iii) unsaturated carboxylic acid monomer, etc., and (C) a monomer copolymerizable with the above monomers in the presence or absence of a thermoplastic resin and/or rubbery polymer while stepwise or continuously varying the ratio of the component (ii) and/or component (iii) to the component (i). A fraction containing <=10wt.% components (ii) and (iii) in total accounts for 1-99wt.% and a fraction containing >10wt.% components (ii) and (iii) in total accounts for 99-10wt.% of the objective copolymer. The average composition of the copolymer satisfies the formulas I and II.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has excellent heat resistance, chemical resistance, mechanical properties, and moldability, and has compatibility or affinity with various non-polar and polar materials. The present invention relates to a method for producing a good copolymer.

<Prior Art> Styrene resins or methyl methacrylate resins have excellent moldability and appearance, and are widely used as vehicle parts, electrical parts, office equipment parts, and the like. However, these resins have the disadvantage of poor heat resistance, and in recent years, in order to improve their heat resistance, resins have been developed that incorporate maleimide monomers, maleic anhydride, methacrylic acid, etc. as heat resistance imparting ingredients. It is being actively progressed.

Furthermore, in order to improve the impact strength of resins incorporating these heat resistance imparting components, for example, compositions of styrene-maleimide copolymers and ABS resins (Japanese Patent Publication No. 61-269
86, JP 58-129048 ft), compositions of styrene-maleimide copolymers and polycarbonates (JP 58-129245), styrene and/or methyl methacrylate-acrylonitrile-maleimide copolymers, Compositions consisting of ABS resin and polycarbonate (Japanese Patent Publication No. 61-174249, Japanese Patent Publication No. 61-174249), compositions of styrene-maleimide copolymers or styrene-acrylonitrile-maleimide copolymers and polyphenylene ether (Japanese Patent Publication No. 61-174249, Japanese Patent Publication No. 61-174249) 60-58257
) etc. have been proposed.

<The problem that the invention is trying to solve> However,
Resins formed by introducing maleimide monomers and the like as described above have very high polarity, and therefore have poor compatibility with materials that are non-polar or have low polarity. This tendency becomes more pronounced as the content of heat resistance imparting components such as maleimide monomers in the resin increases. As a result, it is difficult to obtain a resin composition having the characteristics originally possessed by each resin. For example, a composition of a styrene-maleimide copolymer and polyphenylene ether as disclosed in the above-mentioned Japanese Patent Publication No. 60-58257 has poor compatibility, so it is difficult to obtain a composition with high heat resistance and impact strength.

<Means for Solving the Invention> The present inventors have solved the above-mentioned problems and improved heat resistance, etc.
We have conducted intensive studies to obtain a copolymer that has excellent chemical resistance, mechanical properties, moldability, weather resistance, color development, etc., and has very good compatibility or affinity with various non-polar and polar materials. As a result, a method for producing a copolymer comprising a specific heat resistance-imparting component and having a specific composition distribution was discovered, leading to the present invention.

That is, the present invention provides the following methods: in the presence or absence of a thermoplastic resin and/or a rubbery polymer, either the maleimide monomer (A-1) or the unsaturated carboxylic acid monomer (A-2) one or two monomers (6), and an aromatic vinyl monomer (B-1
), unsaturated nitrile monomer (B-2) and unsaturated carboxylic acid ester monomer CB-8'' In a method for producing a copolymer consisting of a polymerizable monomer (C) and having an average composition (excluding thermoplastic resin and rubbery polymer) represented by formulas (1) and (2), monomer Provide a step of copolymerizing by changing stepwise or continuously the addition ratio of at least one monomer among monomers (B-2) and/or (B-8) to body (B-1). As a result, the total content of monomers (B-2) and (B-8) is 1 to 90% by weight in the area of 10% by weight or less, and 99 to 10% by weight in the area exceeding the content of filO weight%. It has excellent heat resistance, chemical resistance, mechanical strength and moldability, and has good compatibility or affinity with various non-polar and polar materials. A method for producing a polymer is provided.

average composition four X100=1 to 60% by weight (1) (c)+◎+0 The present invention will be explained in detail below.

0 Constituent Components of Copolymer Examples of the thermoplastic resin and/or rubbery polymer that can be used in the production of the copolymer of the present invention include the following.

Polyethylene, polypropylene, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, N-phenylmaleimide Graft polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid and its metal salt copolymer,
Ethylene-(meth)acrylic acid ester copolymers such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, and dimethylaminoethyl, ethylene-(meth)acrylic acid alkyl ester-(meth)acrylic acid copolymers , ethylene-(meth)acrylic acid alkyl ester-maleic anhydride copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer,
Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene-butadiene random or block copolymer, hydrogen Styrene-butadiene random or block copolymer, acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, polyetheramide , polyetheretherketone, polyphenylene sulfide, polysulfone, polyethersulfone, polyphenylene ether, polyoxymethylene, and the like. Particularly preferred are those having a glass transition temperature of 0°C or less.

As the maleimide monomer (A-1), maleimide,
N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-
Phenylmaleimide, N-2,8 or 4-methylphenylmaleimide, N-2,8 or 4-nitylphenylmaleimide, N-2,8 or 4-butylphenylmaleimide, N-2,6-dimethylphenyl maleimide, N
-2,8 or 4-chlorophenylmaleimide, N-2
, 8 or 4-bromophenylmaleimide, N-2゜5
-dichlorophenylmaleimide, N-3,4-dichlorophenylmaleimide, N-2,5-dibromophenylmaleimide, N-3,4-dibromophenylmaleimide,
N-2,4,6-trichlorophenylmaleimide, N-
2,4,6-tribromophenylmaleimide, N-2,
3 or 4-hydroxyphenylmaleimide, N-2,
3 or 4-methoxyphenylmaleimide, N-2,3
or 4-carboxyphenylmaleimide, N-4-nitrophenylmaleimide, N-4-diphenylmaleimide, N-1-naphthylphenylmaleimide, N-4-cyanophenylmaleimide, N-4-phenoxyphenylmaleimide, N- -4-benzylphenylmaleimide, N
-2-methyl-5-chlorophenylmaleimide, N-2
-Methoxy-5-chlorophenylmaleimide is exemplified, and one or more types can be used. Among these, N-aryl-substituted maleimides are particularly preferred.

Examples of the unsaturated carboxylic acid monomer (A-2) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and himic anhydride. Among these, methacrylic acid and maleic anhydride are particularly preferred.

Any one or two of the above maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2) constitute a copolymer as monomer (2).

As the aromatic vinyl monomer (B-1), styrene,
α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene,
3.4-dichlorostyrene, p-bromostyrene, 〇-
Bromostyrene, 2,5-dipromostyrene, 3.4-
Examples include dipromostyrene, cyanostyrene, 2-impropenylnaphthalene, etc., and one or more types can be used. Among these, styrene or α-methylstyrene is usually preferred.

Examples of the unsaturated nitrile monomer (B-2) include acrylonitrile, methacrylonitrile, maleonitrile, and fumaronitrile, and one or more of them can be used. Among these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid ester monomer (B-3) include (meth)acrylates such as methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl, and dimethylaminoethyl; Examples include acrylic acid ester monomers, and mono- and dialkyl esters of unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and hymic acid. One or more types of these can be used. Among these, methyl methacrylate is usually preferred.

One type selected from the above-mentioned aromatic vinyl monomer (B-1), unsaturated nitrile monomer CB-2) and unsaturated carboxylic acid ester monomer (B-8), or Two or more types constitute a copolymer as monomers ◎.

Furthermore, as is clear from formula (1), the above monomer (
A monomer copolymerizable with c) and c) can be used as monomer 0.

As monomer 0, ethylene, propylene, butene-1
, pentene-1,4-methylpentene-1, vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene,
Examples include butadiene, acrylamide, methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinyl ketone, coumaron, indene and acenaphthylene.

0 Average composition The average composition of all the polymers obtained by the method of the present invention is represented by the above formulas (1) and (2).

In formula (1), if the amount of monomer (■) is less than 1% by weight, a copolymer with high heat resistance cannot be obtained;
If it exceeds 0% by weight, not only mechanical strength and processability will decrease, but also compatibility with non-polar or less polar materials will decrease. Particularly preferred amounts of monomer (6) are from 3 to 50% by weight. Furthermore, in formula (2), if the amount of monomer 0 exceeds 50% by weight, the original properties of the copolymer will be lost. The preferred amount of monomer 0 is 0
~30% by weight.

0 composition distribution The copolymer obtained by the method of the present invention has a monomer (B
-2) and (B-8) has a composition distribution in which the total content is 1 to 90% by weight in the region of 10% by weight or less, and 99 to 10% by weight in the region where the content exceeds -110% by weight.

If the copolymer has a total content of monomers (B-2) and (B-8) of 10% by weight or less and is less than 1% by weight, it has poor affinity with non-polar or less polar materials, On the other hand, if the amount exceeds 90% by weight, chemical resistance will be poor.

is 5 to 80% by weight.

Furthermore, in order to improve chemical resistance, color development, affinity with various polar materials, etc., the copolymer must be a monomer (B-2)
It is desirable that the copolymer has a composition distribution such that the total content of (B-8) is 2 to 80% by weight in a region exceeding 20% by weight.

0 Production of copolymer The production process in the present invention involves changing the addition ratio of monomer (B-2) and/or (B-8) to monomer (B-1) stepwise or continuously. This is a copolymerization process.

Specific methods of the manufacturing process include the following methods.

(a) Monomer (B-2) relative to monomer (B-1)
and/or a method in which polymerization is initiated by increasing the addition ratio of (B-8) and polymerization is carried out while gradually lowering the addition ratio.

(1)) Monomer (B-2) relative to monomer (B-1)
) and/or (B-8) in a low addition ratio to start polymerization, and gradually increase the addition ratio in polymerization.

(C) Monomer (B-2) relative to monomer (B-1)
and/or a method of polymerizing while arbitrarily changing the addition ratio of (B-8).

Among the above methods, method (a) is usually preferred.

Further, there are no restrictions on the polymerization method, and any method such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, or a combination thereof can be used. In this case, known polymerization initiators, chain transfer agents, solvents, suspension stabilizers, emulsifiers, pH adjusters, etc. can be used alone or in combination.

The copolymer is produced in the presence or absence of a thermoplastic resin and/or rubbery polymer. When the polymerization is carried out in the presence of the copolymer, the upper limit of the amount of the thermoplastic resin and/or rubbery polymer in the copolymer is preferably 80% by weight or less. Here, especially when the above-mentioned monomers are polymerized in the presence of a rubbery polymer, a graft copolymer having high impact strength can be obtained. The structure of this graft copolymer is not particularly limited, but the weight average particle diameter of the graft copolymer is 0.05.
~10 μm 1 Graft ratio is preferably 10 to 200% by weight. In addition, the intrinsic viscosity of the copolymer is usually 0.2~
1.5 dl/9 is preferred. Here, when the above-mentioned monomers are graft-polymerized in the presence of a thermoplastic resin and/or rubbery polymer, generally all the monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer, and monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer. Some of the polymers form free copolymers. Therefore, the intrinsic viscosity of the copolymer in this case means the intrinsic viscosity of the free copolymer. Note that the intrinsic viscosity is a value measured in a dimethylformamide solution at 30''C.

In addition, the copolymer containing a maleimide monomer component in the present invention is not only a copolymer produced by directly copolymerizing a maleimide monomer and another monomer, but also a copolymer containing maleic anhydride. A copolymer containing methacrylic acid or methyl methacrylate may be imidized by reacting with ammonia, a primary amine, an isocyanate, etc. The copolymer may be converted into a copolymer containing a glutaric anhydride group or a glutarimide group by heat treatment in the presence or absence of the like.

Furthermore, for the copolymer obtained by the method of the present invention,
Antioxidants, heat stabilizers, light stabilizers, lubricants, as necessary.
Plasticizers, antistatic agents, inorganic and organic colorants, blowing agents, inorganic and organic fillers, flame retardants, surface gloss improvers,
A matting agent etc. can be added.

These various additives can be added during the copolymer manufacturing process or in the subsequent processing process.

It should be noted that the copolymer obtained by the method of the present invention can of course be used alone, and since it has a very good affinity with various polar materials, it can be used with glass fiber, metal fiber, carbon fiber, or any of these materials. It can be used as a composite material such as powder, low melting point alloy, calcium carbonate, talc, gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, potassium titanate, etc.

Furthermore, polystyrene, rubber-modified polystyrene, maleic anhydride-styrene copolymer, maleic anhydride-acrylonitrile-styrene copolymer, acrylonitrile-
Styrene copolymer, acrylonitrile-a-methylstyrene copolymer, methachloronitrile-styrene copolymer, methyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate-acrylonitrile-styrene copolymer, Methyl methacrylate-methacrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer, maleimide monomer and aromatic vinyl monomer, unsaturated carboxylic acid, unsaturated carboxylic acid ester, unsaturated nitrile monomer copolymer with one or more parts of one or more other copolymerizable monomers, methyl methacrylate-glutaric anhydride copolymer, methyl methacrylate-styrene-glutaric anhydride copolymer, methacryl Acid methyl-glutarimide copolymer, styrene-acrylonitrile-methacrylic acid copolymer, ABS resin, AES resin, MBS resin, AC9 resin, AAS resin, polyethylene, polypropylene, polybutene-11 ethylene-butene-1 copolymer, Propylene-butene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber,
Maleic anhydride grafted polyolefin, maleimide monomer grafted polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol coffi polymer, ethylene-(meth)acrylic acid and its metal salt copolymer, ethylene -(meth)acrylate methyl, ethyl, propyl, butyl, glycidyl,
(meth)acrylic acid ester copolymers such as dimethylaminoethyl, ethylene-(meth)acrylic acid copolymers,
Ethylene-(meth)acrylic acid ester-(meth)acrylic acid copolymer, ethylene-methacrylic acid ester-
Maleic anhydride copolymer, ethylene-maleimide (N-
7-aryl substituted maleimide) copolymer, ethylene-(meth)acrylic acid ester-maleimide (N-aryl substituted maleimide) copolymer, polytetrafluoroethylene,
Ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene,
Polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene-butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, Polyamide, polyimide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, polyetheramide, polyetheretherketone, polyphenylene sulfide, polysulfone, polyethersulfone, polyphenylene ether, styrene-rubber modified polyphenylene ether, poly Vehicle parts, ship parts, aircraft parts, electrical/electronic parts, building materials, office equipment, power tools, agricultural machinery parts, household goods as one or more resin compositions or laminates with oxymethylene etc. It can be widely used in many fields such as sports and leisure goods.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Note that all parts and percentages shown in the examples are based on weight.

Example 1 In a 20 g reactor equipped with a stirrer and a plate baffle, 70 parts of pure water and 0.0 parts of sodium dodecylbenzenesulfonate were added.
After charging 1 part and 0.05 part of potassium persulfate, the inside of the reactor was purged with nitrogen gas, and the temperature was raised to 75''C while stirring.

To this is added a solution ((l)
solution) was added continuously over 6 hours. At the same time as the addition of this monomer solution was started, 50 parts of pure water and 0.0 parts of potassium persulfate were added.
3 parts and sodium dodecylbenzenesulfonate 1.
Two parts of the aqueous solution were added continuously over a period of 7 hours.

After the addition of the above monomer solution, the following monomer solutions (2) to (6) were successively added over 20 minutes each. Next, 0.2 parts of potassium persulfate was added, and then 20 parts of styrene was continuously added over 2 hours.

Thereafter, it was held at 75°C for 2 hours. Note that t-dodecyl mercaptan was used as a chain transfer agent. The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 1 shows the analysis results during the polymerization process.

0 monomer solution (2) (3) (4)
(5) (6) Acrylonitrile (2)) 4
0 80 20 10 8su, Chiren [owned])
60 70 80 90 97 Added parts
22222 Example 2 50 parts of pure water, 0.1 part of potassium persulfate, and 0.1 part of sodium dodecylbenzenesulfonate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, the mixture was stirred. The temperature was raised to 70°C.

A solution consisting of 24 parts of N-phenylmaleimide, 9 parts of acrylonitrile, 27 parts of styrene and 0.2 parts of t-dodecylmercaptan was continuously added to this over 5 hours.

In addition, at the same time as starting addition of this monomer solution, potassium persulfate o, part a, sodium dodecylbenzenesulfonate 1
．． An aqueous solution consisting of 2 parts and 70 parts of pure water was continuously added over 7 hours.

After adding the above monomer solution, acrylonitrile 6
14 parts of acrylonitrile and styrene were used, and the acrylonitrile/styrene addition ratio at the start and end of addition was changed to 40%/60% and O%/100%, respectively, and continuous addition was carried out over 2 hours. did.

Next, 0.2 parts of potassium persulfate was added, and then 20 parts of styrene was continuously added over 2 hours.

Thereafter, the temperature was raised to 75°C and maintained for 2 hours.

A magnesium sulfate aqueous solution was added to the obtained latex to coagulate it, and the copolymer was recovered.

Table 2 shows the analysis results during the polymerization process.

Example 3 The reactor used in Example 1 was charged with an aqueous solution consisting of 0.1 part of potassium persulfate, 0.2 part of sodium lauryl sulfate, and 60 parts of pure water, and after replacing the inside of the reactor with nitrogen gas, the mixture was stirred. The temperature was raised to 50°C.

First, 3 parts of a solution consisting of 21 parts of N-phenylmaleimide, 49 parts of methyl methacrylate, and 0.2 parts of t-dodecylmercaptan were added to the mixture, and the temperature was raised to 70°C. Then, the remaining monomer solution (67 parts) was continuously added over 6 hours. Simultaneously with the addition of this monomer solution, an aqueous solution consisting of 0.3 parts of potassium persulfate, 1.5 parts of sodium lauryl sulfate, and 60 parts of pure water was continuously added over 8 hours.

After adding the above monomer solution, 10 parts of methyl methacrylate and 10 parts of para-methylstyrene were used, and the addition ratio of methyl methacrylate/para-methylstyrene at the beginning and end of addition was 100%, 1096 and 1096, respectively. The ratio was changed to 0%/100%, and the addition was continued over 2 hours. Next, 0.1 part of potassium persulfate was added, and then 10 parts of paramethylstyrene was continuously added over 1 hour.

Thereafter, the temperature was raised to 75°C and held for 3 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 3 shows the analysis results during the polymerization process.

Example 4 70 parts of pure water, 0.2 parts of potassium persulfate, and 0.3 parts of sodium dodecylbenzenesulfonate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, the mixture was stirred. First, 3 parts of a solution consisting of 25 parts of N-cyclohexylmaleimide, 21 parts of methyl methacrylate, and 14 parts of styrene were added to the mixture, and the temperature was raised to 70°C.

The remaining monomer solution (57 parts) was continuously added to this over 5 hours. Further, an aqueous solution consisting of 50 parts of pure water, 0.2 parts of potassium persulfate, and 1.1 parts of sodium dodecylbenzenesulfonate was continuously added over 8 hours. After adding the above monomer solution, a solution of 9.5 parts of methyl methacrylate and 0.5 parts of methyl acrylate was added over 1 hour, followed by 6 parts of methyl methacrylate and 1 part of styrene.
Using 4 parts, the addition ratio of methyl methacrylate/styrene at the start and end of addition was 60%/40, respectively.
% and 0%/100%, and was added over 2 hours. Then, 10 parts of styrene and 10 parts of a 1% aqueous solution of potassium persulfate were continuously added over 1 hour.

Thereafter, it was held at 70°C for 2 hours. Note that t-dodecyl mercaptan was used as a chain transfer agent. The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 4 shows the analysis results during the polymerization process.

Example 5 70 parts of pure water, 0.2 part of sodium dodecylbenzenesulfonate, and 0.1 part of potassium persulfate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, the mixture was stirred. 3 parts of a mixed solution consisting of 20 parts of N-phenylmaleimide, 14 parts of acrylonitrile, 43 parts of styrene, and 3 parts of methacrylic acid were added to the mixture, and the temperature was raised to 70°C. To this, the remaining monomer solution (77 parts) and an aqueous solution consisting of 3 parts of potassium persulfate, 0.8 parts of sodium dodecylbenzenesulfonate, and 50 parts of pure water were continuously added over 6 hours.

Subsequently, 4 parts of acrylonitrile and 16 parts of styrene were used, and the ratio was changed so that the acrylonitrile/styrene addition ratio at the start and end of addition was 40%/60% and 0%/100% for 2 hours. It was added continuously.

Thereafter, the temperature was raised to 75°C and held for 3 hours.

Note that t-dodecyl mercaptan was used as a chain transfer agent. The obtained latex was coagulated with magnesium sulfate, and the copolymer was recovered. Table 5 shows the analysis results during the polymerization process.

Example 6 60 parts of pure water, 0.1 part of potassium persulfate, and 0.1 part of sodium lauryl sulfate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, N was added while stirring. −
First, 3 parts of a solution consisting of 20 parts of 2-chlorophenylmaleimide, 10 parts of acrylonitrile, 32 parts of methyl methacrylate, 8 parts of styrene, and 0.3 parts of t-dodecylmercaptan were charged, and the temperature was raised to 70°C. Add to this the remaining monomer solution (67 parts), 60 parts of pure water, 0.2 parts of potassium persulfate, and 1.2 parts of sodium lauryl sulfate.
of the aqueous solution was added continuously over 5 hours.

Then, using 6 parts of a solution consisting of 25% acrylonitrile and 75% methyl methacrylate and 12 parts of styrene, the addition ratio of acrylonitrile-methyl methacrylate solution/styrene at the start and end of addition was 60%/40%, respectively. The mixture was continuously added over a period of 2 hours while changing the ratio so that the ratio was θ%/100%. Next, 0.1 part of potassium persulfate was added, and then 10 parts of styrene was continuously added over 1 hour.

Thereafter, the temperature was raised to 75°C and held for 2 hours.

The obtained latex was coagulated with an aqueous magnesium sulfate solution, and the copolymer was recovered. Table 6 shows the analysis results during the polymerization process.

Example 7 70 parts of pure water, 0.2 part of sodium dodecylbenzenesulfonate and 0.2 part of potassium persulfate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, methacrylic acid 14 and 56 parts of styrene, and the temperature was raised to 70°C. The remaining monomer solution (65 parts) was continuously added to this over 6 hours. Further, at the same time as the addition of this monomer solution was started, an aqueous solution consisting of 50 parts of pure water, 1.5 parts of sodium dodecylbenzenesulfonate, and 0.3 parts of potassium persulfate was continuously added over 8 hours.

After adding the above monomer solution, using 3 parts of acrylonitrile and 17 parts of styrene, the addition ratio of acrylonitrile/styrene at the start of addition and after the end of addition was 30, respectively.
%/70% and O%/100% over 2 hours.

Then, after adding 0.1 part of potassium persulfate, 10 parts of styrene was continuously added over 1 hour. then 75°
The temperature was raised to C and held for 2 hours. The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered.

Note that t-dodecyl mercaptan was used as a chain transfer agent. Table 7 shows the analysis results during the polymerization process.

Example 8 70 parts of pure water, 0.1 part of potassium persulfate, 0.2 part of sodium lauryl sulfate, and 0.2 part of potassium alkenylsuccinate were charged into the reactor used in Example 1, and the pH of the aqueous phase was adjusted.
was adjusted to 6.8 with a potassium dihydrogen phosphate-disodium hydrogen phosphate aqueous solution. Next, the inside of the reactor was replaced with nitrogen gas, and then the temperature was raised to 65° C. while stirring.

A solution consisting of 5 parts of acrylonitrile and 15 parts of α-methylstyrene was added to this, and the temperature was raised to 75° C. over 1 hour. Next, a solution consisting of 15 parts of N-phenylmaleimide, 6 parts of acrylonitrile and 24 parts of α-methylstyrene was continuously added over 5 hours, and then 0.5 parts of N-phenylmaleimide and 4.5 parts of acrylonitrile were added.
of the solution were added continuously over a period of 30 minutes. Thereafter, it was held at 75°C for 2 hours. (First stage) At the same time as starting the continuous addition of the above monomer solution, potassium persulfate 0,
An aqueous solution consisting of 2 parts of sodium lauryl sulfate, 0.7 parts of sodium lauryl sulfate, 0.7 parts of potassium alkenylsuccinate, and 70 parts of pure water was continuously added over 6 hours.

Then, using 3 parts of acrylonitrile and 12 parts of styrene, the acrylonitrile /
The addition ratio of styrene is 4. It was added over 2 hours so that the ratio was θ%/60% and θ%/100%. (
2nd stage) Next, 15 parts of styrene was continuously added over 1 hour.

It was then held at 75°C for 2 hours.

(Step 3) Pentaerythritol tetrakis (thioglycolate) was used as a chain transfer agent. Further, from the start of the second stage polymerization, an aqueous solution consisting of 10 parts of pure water, 0.2 parts of sodium lauryl sulfate, and 0.2 parts of potassium persulfate was added over a period of 3 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 8 shows the analysis results during the polymerization process.

Example 9 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.2 parts of lactose were added to the reactor used in Example 1, and then butyl acrylate rubber was added. Latex (weight average particle size 0.4 μm 1 gel content 77
%, solid content 40%, emulsifier sodium lauryl sulfate, p
After charging 50 parts (solid content equivalent) of H6,1), the inside of the reactor was purged with nitrogen gas, and the temperature was raised to 70''C while stirring.

To this was added a solution consisting of 3 parts of N-phenylmaleimide, 6 parts of acrylonitrile, 16 parts of α-methylstyrene, and 0.2 parts of ethylene glycol thiodiglycolate, as well as 0.5 parts of sodium lauryl sulfate and 0 parts of cumene hydroperoxide. An aqueous solution consisting of .3 parts and 20 parts of pure water was continuously added over 5 hours.

Next, using 2 parts of acrylonitrile and 8 parts of styrene, the addition ratio of acrylonitrile/styrene at the start and end of addition was 40%/60% and 0%, respectively.
/100% over 1 hour, and then 15 parts of styrene was further added continuously over 2 hours.

Thereafter, the temperature was raised to 75°C and held for 2 hours. In addition, at the same time as the addition of acrylonitrile and styrene was started, 0.1 part of potassium persulfate and 0 part of sodium lauryl sulfate were added.
．． An aqueous solution consisting of 1 part of pure water and 10 parts of pure water was continuously added over 3 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution to obtain a copolymer with a graft ratio of 47%. Table 9 shows the analysis results during the polymerization process.

Example 10 In the reactor used in Example 1, 30 parts of pure water, 0.1 part of potassium persulfate, 0.1 part of sodium lauryl sulfate, and polybutadiene latex (rubber weight average particle size 0) were added.
．． 45 μm, gel content 77%, solid content 41%) 25 parts (solid content equivalent) and styrene-butadiene copolymer latex (rubber weight average particle diameter 0.21 μm 1 Styrene content 24%, gel content 81%, solid content After charging 25 parts (solid content equivalent) of 45%), the inside of the reactor was purged with nitrogen gas, and the temperature was raised to 75° C. with stirring.

To this, a solution consisting of 9 parts of N-phenylmaleimide, 6 parts of acrylonitrile and 15 parts of styrene and 2 parts of pure water were added.
An aqueous solution consisting of 0 parts of potassium persulfate, 0.2 parts of potassium persulfate, and 0.5 parts of sodium lauryl sulfate was continuously added over 4 hours. (First stage) Subsequently, 1.5 parts of acrylonitrile and 3 parts of styrene were added.
A solution consisting of 5 parts was added over 30 minutes. (Second stage) Next, a solution consisting of 0.5 parts of acrylonitrile and 4.5 parts of styrene was added over 30 minutes. (Third stage) Next, 0.2 parts of potassium persulfate was added, and then 10 parts of styrene was added over 1 hour. Thereafter, it was held at 75°C for 2 hours. (Fourth step) Terpircin was used as a chain transfer agent. The obtained latex was coagulated with magnesium sulfate, and a copolymer with a gellast percentage of 57% was recovered. Table 10 shows the analysis results during the polymerization process.

Comparative Example 1 70 parts of pure water, 0.1 part of sodium dodecylbenzenesulfonate and 0.1 part of potassium persulfate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, the mixture was stirred. The temperature was raised to 70°C.

To this was added a solution consisting of 20 parts of N-phenylmaleimide, 20 parts of acrylonitrile, 60 parts of styrene and 0.3 parts of t-dodecylmercaptan, 50 parts of pure water, 0.8 parts of sodium dodecylbenzenesulfonate and 0.2 parts of potassium persulfate. of the aqueous solution was added continuously over 5 hours.

It was then held at 70°C for 2 hours. The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymers shown in Table 11 were recovered.

Comparative Example 2 50 parts of pure water, 0.1 part of potassium persulfate, and 0.1 part of sodium dodecylbenzenesulfonate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, the mixture was stirred. The temperature was raised to 70°C.

A solution consisting of 24 parts of N-phenylmaleimide, 9 parts of acrylonitrile, 27 parts of styrene and 0.2 parts of t-dodecylmercaptan was continuously added to this over 3 hours.

Also, at the same time as the addition of this monomer solution started, 0.2 parts of potassium persulfate and sodium dodecylbenzenesulfonate were added.
An aqueous solution consisting of 1.2 parts of aluminum and 70 parts of pure water was continuously added over 5 hours.

After adding the above monomer solution, acrylonitrile 1
A solution consisting of 2 parts of styrene, 28 parts of styrene, and 0.2 parts of t-dodecylmercaptan was continuously added over a period of 2 hours. Thereafter, the temperature was raised to 75°C and held for 2 hours. The obtained latex was coagulated with an aqueous magnesium sulfate solution, and the 11th
The copolymers shown in the table were recovered.

Comparative Example 3 70 parts of pure water, 0.5 part of sodium dodecylbenzenesulfonate and 0.2 part of potassium persulfate were charged into the reactor used in Example 1, and after purging the inside of the reactor with nitrogen gas, the reactor was stirred. 1 part of methacrylic acid, 3 parts of acrylonitrile, 94 parts of styrene, and 0.0 parts of t-dodecylmercaptan.
Five parts of the three parts solution were added and the temperature was raised to 70''C.

To this, the remaining monomer solution and an aqueous solution consisting of 50 parts of pure water, 1.5 parts of sodium dodecylbenzenesulfonate, and 0.8 parts of potassium persulfate were continuously added over 8 hours.

Thereafter, the temperature was raised to 75°C and held for 2 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymers shown in Table 11 were recovered.

The analysis results of the copolymers obtained in Examples 1 to 10 and Comparative Examples 1 to 3 are summarized in Table 11. The abbreviations shown in Tables 1 to 11 represent the following, respectively. Furthermore, the composition of the copolymer was determined from elemental analysis of carbon, hydrogen, nitrogen, and oxygen and mass balance in the copolymer manufacturing process.

NPMI: N-phenylmaleimide CHMI: N-cyclohexylmaleimide CPMI: N
-2-Chlorophenylmaleimide MAA: Methacrylic acid AN: Acrylonitrile MMA: Methyl methacrylate MA Methyl diacrylate S: Styrene AMS: α-Methylstyrene PMS: Paramethylstyrene SBR: Styrene-butadiene copolymer rubber BR: Polybutadiene rubber BAR: Polybutyl acrylate rubber [η] Intrinsic viscosity measured in dimethylamide solution at 30°C Unit: dl/f Next, in order to investigate the characteristics of the copolymers produced in each example and comparative example, the following test examples were used. I conducted a test. The thermoplastic resin and rubbery polymer for blending used in the test were the following polymers A to M.

30 parts of ferrous sulfate heptahydrate, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.3 parts of dextrose, and then polybutadiene latex (rubber weight average particle size 0.47 μm, gel content 79%, solid content 42%) 60
After charging the reactor with nitrogen gas, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70°C while stirring.

To this, a mixed solution consisting of 15 parts of acrylonitrile, 35 parts of styrene, and 0.3 parts of t-dodecyl mercaptan, and 1.2 parts of alkenyl co/% potassium phosphate, t-
Butyl hydroperoxide 0.3 parts and pure water 80 parts
of the aqueous solution was added continuously over a period of 3 hours. Thereafter, the mixture was held at 75° C. for 2 hours to obtain latex with a polymerization rate of 99.1%. The obtained latex was coagulated with magnesium sulfate, and a polymer having a grafting rate of 42% and an ungrafted copolymer having an intrinsic viscosity of 0.47 dl/I was recovered.

Polymer B (AAS) Butyl acrylate rubber latex (weight average particle size 0.3
μm1 gel content 79%, solid content 42%) 50 parts (in terms of solid content) was used as a rubber component, and polymerized according to the following procedure. A polymer having an intrinsic viscosity of 0.52 dll'l was obtained.

Polymer C (ABSM) 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.3 parts of dextrose were added to the reactor used in Example 1, and then After charging 60 parts (in terms of solid content) of acrylonitrile-butadiene rubber latex (rubber weight average particle size 0.31 μm, gel content 77%, acrylonitrile content 30%, solid content 41%), the inside of the reactor was filled with nitrogen gas. 70°C under stirring.
The temperature was raised to ℃. To this, the following monomer solution containing t-dodecyl mercaptan was continuously added over 4 hours for polymerization. On the other hand, simultaneously with the start of addition of the monomer solution, the following emulsifier-polymerization initiator aqueous solution was continuously added over 4 hours. Thereafter, the mixture was held at 75° C. for 2 hours to obtain latex with a polymerization rate of 98.9%. The obtained polymer latex was coagulated with calcium chloride, and a polymer having a graft ratio of 41% and an intrinsic viscosity of the ungrafted copolymer of 0.5161/l was recovered.

0 Monomer solution (part) Acrylonitrile・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 5 Methyl methacrylate・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・28 Styrene ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・120 emulsifier-polymerization initiator aqueous solution (part) pure
water ················
・・・・・・・・・・・・・・・・・・・・・ 30 Sodium dehydroabietate ・・・・・・・・・・・・・
・・・・・・・IS cumene hydroperoxide・・・・・・・・・・・・・・・・・・0.8 Polymer D
(MBS) 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium birophosphate, and 0.3 parts of dextrose were added to the reactor used in Example 1, and then styrene-butane was added. Gen rubber latex (rubber weight average particle diameter 0.4
7 μm, gel content 77%, styrene content 25%, solid content 41%) 50 parts (solid content equivalent) were charged, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70'C while stirring. .

To this, the following monomer solution containing t-dodecyl mercaptan was continuously added over 4 hours for polymerization. on the other hand,
Simultaneously with the start of addition of the monomer solution, the following emulsifier-polymerization initiator aqueous solution was continuously added over 4 hours. After that, 75
The mixture was kept at ℃ for 2 hours to obtain a latex with a polymerization rate of 98.9%. The obtained polymer latex was coagulated with calcium chloride, resulting in a graft ratio of 45% and an ungrafted copolymer of 0.
49 dl/f of polymer was recovered.

0 Monomer solution (part) Methyl methacrylate 30 Styrene 200 Emulsifier-polymerization initiator aqueous solution (part) Pure water
30 Sodium dehydroabietate 1.5 t-Butyl hydroperoxide 0.3 Polymer E (AES) In the reactor used in Example 1, 0.5 block type polyether dispersant (Pluronic F68 manufactured by Asahi Denka Co., Ltd.) was added. 550 parts of pure water dissolved in 550 parts of pure water, and ethylene-propylene-ethylidene norbornene ternary copolymer comb chopped into 4 to 6 meshes (iodine number 21.1, Mooney viscosity at 100°C 76, propylene content 46.0 weight) %) was charged and stirred to suspend. Next, a monomer mixture of 40 parts of acrylonitrile and 75 parts of styrene containing 3 parts of t-butylperoxypivalate and 0.05 part of p-quinone was added as a polymerization initiator, and steam was immediately blown into the jacket of the autoclave to raise the temperature. Start heating. 20
After a few minutes, the temperature reached 100"C, and the temperature was kept at 100"C for 1 hour.
The polymerization reaction was carried out while maintaining the temperature at ``C''. As a result, the grafting rate was 71%, and the intrinsic viscosity of the ungrafted copolymer was 0.57 dl.
A polymer of /11 was obtained.

Polymer F Polystyrene (Japan Polystyrene, Nisbright 4) Polymer G High impact polystyrene (Japan Polystyrene,
Varnish Bright 500SB) Polymer H Polycarbonate (Otodai Kasei, Panlite L
-1250) Polymer I Polyamide (Mitsubishi Kasei, Tsubamitsudo 1015
G30) Polymer J Ethylene-glycidyl methacrylate copolymer (Jumin Chemical Co., Ltd., Bondfust 7-St 2B) Polymer K Polyester (Toyobo Co., Ltd., Pelprene P40H
) Polymer L Styrene-butadiene broth copolymer (Shell Chemical, Kraton Polymer M Acrylonitrile-styrene copolymer (Nippon Steel Chemical, Estyrene AS Test Examples 1 to 12', Comparative Test Examples 1 to 7 Examples and Comparative Examples Each of the copolymers obtained above or these copolymers and other thermoplastic resins were blended in the proportions shown in Table 12, and triethylene glycol-bis[8-(3- t-butyl-
30.1 parts of 5-methyl-4-hydroxyphenyl)propionate, 0.1 part of dilauryl-3,3'-thiodipropionate, and 0.1 part of (2°4-di-t-butylphenyl)pentaerythritol diphosphite. 2 parts and 0.2 parts of ethylene bis stearamide as a lubricant were added, and while devolatilizing in a vented twin-screw extruder,
The mixture was kneaded at 00°C and pelletized.

The total amount of residual monomers in these pellets was all 0.2% or less.

The pellets were molded using an injection molding machine at 250 to 320''C to prepare test pieces, and their physical properties were measured. The results are shown in Table 12.

In addition, the physical properties were measured by the following method.

Izot impact strength with 0 notches (abbreviated as NI) 2% inch thickness test piece, measured value at 28°C.

0 Heat Deformation Temperature (abbreviated as IDT): Value measured on inch thick test piece, 264 psi load, without annealing.

0 Solvent resistance: After immersing the test piece in gasoline at 30°C for 24 hours,
The state of rough skin etc. on the surface was observed with the naked eye.

Test Examples 13 to 26 and Comparative Tests, Test Examples 8 to 16 Each copolymer obtained in Examples and Comparative Examples or these and other thermoplastic resins or rubbery polymers were mixed in the proportions shown in Table 13. In addition, each composition was mixed with the following compounding ingredients (the amount added is the number of parts per 100 parts of the resin composition) using a Henschel mixer, and then pelletized by the method of Test Example 1 above, and a test piece was obtained. were prepared and their physical properties were measured. The results are shown in Table 13.

0 compounding agent 1) 2-t-butyl-6-(1'-t-butyl-5'-
Methyl-2'-hydroxybenzyl)-4-methylphenylacrylate 0.2
Part 2) Trisnonylphenyl phosphite...0
．． Part 2 B) 2-(8,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1°2
．． 2,6,6-bentamethyl-4-piperidyl)...
・・・・・・・・・・・・・・・・・・・・・・・・
...0.3 parts 4) Ethylene bisstearamide ...0.2 parts 5) Calcium stearate ...・・・・・・
......0.3 part <Effect of the invention> As is clear from the results in Tables 12 and 13, the copolymers produced by the method of the present invention have various non-polar and polar It has good compatibility or affinity with the material,
Shows excellent heat resistance, mechanical strength, and solvent resistance (chemical resistance).

Claims (1)

[Claims] 1. Maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic resin and/or rubbery polymer. Any one or two monomers (A) and an aromatic vinyl monomer (B
-1), one or more monomers (B) selected from unsaturated nitrile monomers (B-2) and unsaturated carboxylic acid ester monomers (B-3) and a monomer (C) copolymerizable with these, and its average composition (
Excludes thermoplastics and rubbery polymers. ) is the formula (1)
In the method for producing a copolymer represented by (2), the addition ratio of monomer (B-2) and/or (B-3) to monomer (B-1) is adjusted stepwise or continuously. By providing a copolymerization step in which the total content of monomers (B-2) and (B-3) is 10% by weight or less, it is 1 to 90% by weight, and the content exceeds 10% by weight. A method for producing a copolymer, characterized in that the copolymer has a composition distribution of 99 to 10% by weight in the region. Average composition (A)/[(A)+(B)+(C)]×100=1-6
0% by weight (1) (C)/[(A)+(B)+(C)]×
100 = 0 to 50% by weight (2) 2, the copolymer contains 5 to 80% by weight in a region where the total content of monomers (B-2) and (B-3) is 10% by weight or less. 95 to 20% by weight in the region exceeding 10% by weight, and the content is 20% by weight
2. The method for producing a copolymer according to claim 1, wherein the copolymer has a composition distribution in a region exceeding 2 to 80% by weight.