JPS63221152A - Copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, chemical resistance, compatibility with a (non)polar material, etc., by copolymerizing a maleimide monomer and/or an unsaturated carboxylic acid monomer with a specified monomer and another monomer copolymerizable therewith. CONSTITUTION:A monomer mixture is obtained by mixing 1-60wt.% maleimide monomer (a) (e.g., N-aryl-substituted maleimide) and/or an unsaturated carboxylic acid monomer (b) (A) (e.g., methacrylic acid) with at least one monomer (B) selected from among an aromatic vinyl monomer (c) (e.g., styrene), an unsaturated nitrile monomer (d) (e.g., acrylonitrile) and an unsaturated carboxylic ester (e) (e.g., methyl methacrylate) and 0-50wt.% monomer (C) copolymerizable therewith. This mixture is copolymerized in the presence (absence) of a thermoplastic resin and/or a rubbery polymer to obtain the title composition comprising 1-70wt.% copolymer of a total content of component A, component (d) and component (e) <=7wt.% and 99-30wt.% copolymer of said content >=7wt.%.

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. This invention relates to a good copolymer composition.

<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 with maleimide monomers, maleic anhydride, methacrylic acid, etc. introduced as heat resistance imparting ingredients have been developed. Development is actively underway.

Furthermore, for the purpose of improving the impact strength of resins into which these heat resistance imparting components are introduced, for example, compositions of styrene-maleimide copolymers and polycarbonate (JP-A-58-1999-1) have been developed.
129245), styrene and/or methyl methacrylate-acrylonitrile-maleimide copolymer,
Compositions consisting of ABS resin and polycarbonate (Japanese Patent Publication No. 61-50976), compositions of styrene-maleimide copolymers, styrene-acrylonitrile-maleimide copolymers, and polyphenylene ether (Japanese Patent Publication No. 61/1989)
-174249) or compositions of these with impact-resistant polystyrene or styrene-butadiene block copolymers (
Special Publication No. 6O-58257) etc. have been proposed.

<The problem that the invention is trying to solve> However,
Resins made by introducing maleimide monomers etc. as mentioned above have very high polarity. Poor compatibility with materials with small 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 composition that has the characteristics originally possessed by each resin.

<Means for solving the invention> The present inventors solved the above-mentioned problems and improved heat resistance, etc.
As a result of intensive studies to obtain a composition that has excellent chemical resistance, mechanical properties, and moldability, and has very good compatibility or affinity with various non-polar and polar materials, we have developed a specific heat resistance-imparting component. We have discovered a copolymer composition consisting of the following and having a specific composition distribution, leading to the present invention.

That is, the present invention provides a method for preparing a maleimide monomer (A-1) and an unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic resin and/or a rubbery polymer.
Any one or two monomers (A), an aromatic vinyl monomer (B-1), an unsaturated nitrile monomer (B
-2) and unsaturated carboxylic acid ester monomer (B-
3) one or more monomers (B
) and a copolymer obtained by polymerizing a monomer IcI copolymerizable with these, the average composition of the composition (excluding thermoplastic resin and rubbery polymer).

) is a copolymer composition represented by Nifil and (2), and the monomers (~, (B-2) and (B-3
), the total content of which is 01-70% by weight of a copolymer with a total content of 7% by weight or less and 099-30% by weight of a copolymer with a total content of more than 7% by weight. be.

○Copolymer The present invention will be explained in detail below.

Examples of the thermoplastic resin and/or rubbery polymer that can constitute the copolymers (1) and (2) of the present invention include the following.

Polystyrene, rubber-modified polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, methacrylonitrile-styrene copolymer, polymethyl methacrylate, methyl methacrylate
Styrene copolymer, methyl methacrylate-acrylonitrile-styrene copolymer, ABS resin, AES resin, M
BS resin, AC3 resin, AAS resin, polyethylene, polypropylene, polybutene-1, ethylene-butene-1
Copolymer, propylene-butene-1 copolymer, propylene-ethylene flock copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, N-
Substituted maleimide graft polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer, ethylene-
Vinyl alcohol copolymers, ethylene-(meth)acrylic acid and its metal salt copolymers, ethylene-(meth)acrylic acid esters such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, and dimethylaminoethyl. Polymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester-(meth)
Acrylic acid copolymer, ethylene-(meth)acrylic acid ester-maleic anhydride copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoro Ethylene-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,
polyether ester, polyether ester amide,
One or more of polyether amide, polyether ether ketone, polyphenylene sulfide, polysulfone, polyether sulfone, polyphenylene ether, styrene-rubber modified polyphenylene ether, polyoxymethylene, and the like. Special glass transition temperature O℃
The following rubbery polymers are preferably used.

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-2,3 or 4-methylphenylmaleimide, N-2,8 or 4-ethylphenylmaleimide, N-2,8 or 4-butylphenylmaleimide, N-2,6-dimethylphenylmaleimide,
N-2,3 or 4-chlorophenylmaleimide, N
-2, 8 or 4-bromophenylmaleimide, N-2
゜5-dichlorophenylmaleimide, N-8,4-dichlorophenylmaleimide)', N-2,5-dibromophenylmaleimide, N-814-dibromophenylmaleimide, N-2,4,6-trichlorophenylmaleimide, N -2, 4.

6-dribromophenylmaleimi)', N-2.

ヱ=≠=##N-2,3 or 4-carboxyphenylmaleimide, N-4-nitrophenylmaleimide, N-
4-diphenylmaleimide, N-1-naphthylphenylmaleimide, N-4-cyanophenylmaleimide, N-
4-phenoxyphenylmaleimide, N-4-pendylphenylmaleimide)', N-2-methyl-miyalorophenylmaleimide, N-2-methoxy-5-chloro especially N-
Aryl-substituted maleimides are 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-mentioned maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2) can be used as a monomer (...) to form a copolymer (■) and/or (■). It is an essential component in the copolymer composition.

As the aromatic vinyl monomer (B-1), styrene,
α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, O-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene,
8.4-dichlorostyrene, p-bromostyrene, 〇-
Bromostyrene, 2,5-dipromostyrene, 8.4-
Examples include dipromostyrene, cyanostyrene, 2-impropenylnaphthalene, etc., and one or more types can be used. Among these, styrene or α-methylstyrene is usually preferred.

Unsaturated 2) IJ monomers (B-2) include acrylonitrile, methacrylonitrile, maleonitrile,
Examples include fumaronitrile, and one or more types can be used. Among these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid ester monomer (B-8) include (meth)acrylates such as methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl, and dimethylamine ethyl; Examples include acrylic/lz acid-1-ster 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 (B-2), and unsaturated carboxylic acid ester monomer (B-3) Alternatively, two or more monomers (as Bl, constitute the copolymer (1) and/or (2), and are essential components in the copolymer composition.

Furthermore, as is clear from formula (1), the above monomer (
Monomers copolymerizable with Al and β) can be used as monomers C).

Monomer (C) includes ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, butadiene, acrylamide. , methacrylamide,
Examples include vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinyl ketone, coumaron, indene and acenaphthylene.

As mentioned above, the copolymer composition of the present invention has its structural unit (1), average composition ratio (11), and composition distribution surface).
are specified respectively.

That is, from the standpoint of the structural unit (1), the maleimide monomer (A-1) and the unsaturated carboxylic acid monomer ( A-2) any one or two monomers (
Al and 1 selected from aromatic vinyl monomer (B-1), unsaturated nitrile monomer (B-2) and unsaturated carboxylic acid ester monomer (B-9) It is defined as a composition consisting of a copolymer obtained by polymerizing monomers (Bl and monomer C copolymerizable with these) with a species or two or more species, and the average composition ratio side is From an aspect, it is defined as a composition whose average composition (excluding thermoplastic resin and rubbery polymer) is within the range represented by formulas (1) and (2). Furthermore, from the perspective of compositional right curve), the monomers (~, (B-2) and (B-3)
Copolymers with a total content of 7% by weight or less 01-70% by weight and copolymers exceeding 7% by weight 099-30% by weight
It is stipulated that

In formula (1) showing the average composition ratio of the copolymer composition, if the amount of monomer (5) is less than 1% by weight, it is difficult to obtain a copolymer composition with high heat resistance; If it exceeds % by weight, not only the affinity will be poor, but also the mechanical strength and processability of the composition will be reduced. The monomer (A
) is 3 to 50% by weight.

Further, the amount of copolymerizable monomer C) in formula (2) is 5
If it exceeds 0% by weight, the properties of the copolymer composition will be lost. A particularly preferred amount of monomer C) in formula (2) is 0 to 30% by weight.

Furthermore, in stipulating the composition distribution of the copolymer composition, copolymer (2) in which the total content of the monomers (At, (B-2) and (B-3) is 7% by weight or less is 1% by weight). If the amount is less than 99% by weight (copolymer 0 exceeds 99% by weight), the compatibility or affinity with non-polar or less polar materials will be poor, while if the amount exceeds 70% by weight (less than 30% by weight ), poor chemical resistance.

From the viewpoint of the properties of the composition, it is preferable that the copolymer content is 05 to 60% by weight and the copolymer content is 095 to 40% by weight. In particular, monomers GAI, (B-j) and ( B
-2 to 8 with a total content of more than 15% by weight of 3)
Compositions containing 0% by weight are preferred.

1, the copolymer composition contains a specific monomer ((A
t, (B-2) and (B-3)] copolymer ■ whose content is 7% by weight or less and copolymer ■ whose content exceeds 7% by weight
However, such a composition can be prepared not only by the method of mixing a copolymer with a low content of a specific monomer and a copolymer with a high content of a specific monomer, but also by the method of mixing a copolymer with a low specific monomer content and a copolymer with a high specific monomer content. By changing the proportion of monomers, it is possible to obtain a necessarily wide compositional distribution, that is, a composition in which low and high specific monomer contents coexist.

Particularly preferred are compositions obtained by the latter method. Furthermore, specific examples include a method of widening the composition distribution by changing the addition ratio within the monomer stepwise or continuously; −
There is a method of widening the composition distribution by changing the addition ratio stepwise or continuously in 3).

In addition, copolymers (1) and/or (2) are copolymers obtained by polymerizing the above monomers in the presence or absence of a thermoplastic resin and/or a rubbery polymer; in this case, The proportion 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 size of the graft copolymer is 0.05 to 10μ.
m, and a grafting ratio of 10 to 150% by weight is preferred. Further, the intrinsic viscosity of the copolymer composition is usually 0.3 to 1
．． 5 de/f 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 refers to the intrinsic viscosity of the free copolymer. Note that the intrinsic viscosity is a value measured in a dimethylformamide solution at 30°C.

Note that the copolymer composition of the present invention contains a thermoplastic resin and/or
Alternatively, a copolymer obtained by polymerizing the above monomer in the absence of a rubbery polymer and a copolymer obtained by polymerizing the above monomer in the presence of a thermoplastic resin and/or a rubbery polymer. It may also be a mixture of copolymers.

Copolymer compositions can be produced by various polymerization methods. Namely, bulk polymerization, suspension polymerization, bulk-suspension polymerization,
It can be produced by emulsion polymerization, solution polymerization, and a combination thereof. In addition, a copolymer containing a maleimide monomer component, which is one of the constituent components of the copolymer composition, is produced by directly copolymerizing a maleimide monomer and a copolymerizable monomer. Of course, copolymers containing maleic anhydride can be mixed with ammonia, primary amines,
It may be imidized by reacting with isocyanate ester, etc. Furthermore, a copolymer containing methacrylic acid or methyl methacrylate is heat-treated in the presence or absence of ammonia, a primary amine, etc., and anhydrous The following coloring agents and one or more organic compounding agents can be added as constituent components of the co-composition containing a glutaric acid group or a glutarimide group. Moreover, these various compounding agents can be added during the manufacturing process of the copolymer and/or copolymer composition or in the subsequent processing process, depending on the purpose of use.

The coloring agent that can be used in the copolymer composition of the present invention is preferably one or more selected from the following from the viewpoint of thermal stability. That is, the colorant is a color ink x (The
5ociety of Dyers and Co1ou
rists (UK) and TheAmerican
As5ociation of Textile Ch
Pigment Red 101. Pigment Red 102, Pigment Red 1108, Pigment? 22, Pigment Red 149, Solvent Red 111, Solvent Red 151, Solvent Red 179, Pigment Orange 20, Solvent Orange 60. Pigment Yellow 37, Pigment Yellow 5
3. Pigment Yellow 183 Solvent Yellow 33
, Pigment Brown 6, Pigment Brown 7, Pigment Brown 11, Pigment Brown 24, Pigment Green 14, Pigment Green 19, Pigment Green 36, Pigment Blue 15, Pigment White 4, Pigment White 6, Pigment White 7, Pigment White 21, Pigment black 10
, Disperse Violet 26 and number 7750
0 etc. are preferably used.

Among these colorants, if Pigment White 4 and/or Pigment White 7 is used in combination with one or more colorants other than these, a product that is even more resistant to discoloration due to heat can be obtained. It will be done.

Note that the particle size of the colorant is preferably fine particles of 0.5 μm or less.

There is no limit to the amount of the colorant added, but it is usually preferably in the range of o, oooi to 20 parts by weight per 100 parts by weight of the copolymer composition. These can be colored in various tones. Further, the colorant can be in various forms such as powder, paste, masterbatch, dry color, and moisturizing colorant.

There are no particular limitations on the type of organic stabilizer that can be used in the copolymer composition of the present invention, but examples include phenol-based, sulfur-based, phosphorus-based, amine-based, benzophenone-based, salicylate-based, benzotriazole-based, and hydrazine-based stabilizers. One or more types selected from epoxy-based and epoxy-based materials are used. Particularly effective against heat and light when one or more of phenol, sulfur, and phosphorus types are used in combination with one or more of amine, benzophenone, salicylate, hydrazine, and benzotriazole types. is large. Note that the amount of these added is o, oi ~3 parts by weight.

As the lubricant, the following are preferably used.

Paraffin having 12 to 70 carbon atoms and molecular weight 1.000
~8,000 low molecular weight polyethylene, carbon number 8-80
fatty acid, fatty acid amide having 8 to 80 carbon atoms, and fatty acid amide having 8 to 80 carbon atoms.
Alkylene bis II & fatty acid amide synthesized from 30 fatty acids and alkylene diamines such as methylene diamine and ethylene diamine, fatty acids with 8 to 30 carbon atoms and 1 carbon number
~20 alcohol esters, di- to tetravalent metal salts of fatty acids having 8 to 30 carbon atoms, fatty alcohols having 8 to 30 carbon atoms, naphthenic acids having 8 to 30 carbon atoms and their di- to tetravalent metal salts, polyethylene Examples include glycol-based, polyglycerol-based, and silicone-based lubricants.

In view of the physical property balance of the final copolymer composition, alkylene bis fatty acid amides, divalent metal salts of fatty acids having 12 to 30 carbon atoms, and silicone lubricants are particularly preferred. In these lubricants, l is 0.01 to 3 parts by weight.

As fillers or reinforcing agents, asbestos, alumina,
Attapulgite, kaolin clay, silicic acid, calcium silicate, diatomaceous earth, slate powder, sericite, quartz powder, zirconia, boron nitride, silicon nitride, calcium carbonate, magnesium carbonate, talc, boron carbide, silicon carbide, titanium Potassium acid, feldspar powder, molybdenum disulfide, pallite, vermiculite, gypsum, waxite clay, glass powder, glass bulbs, glass fiber, nickel chromium, chromium alloy, stainless steel, tanksten alloy, beryllium, molybdenum, aluminum, lead , tin, copper, gold, silver, platinum, and alloys of these metals (including low-melting point alloys), as well as fibers, alumina fibers, carbon fibers, and the like. Among these, powdered ones generally have a particle size of 0.
．． Those with a fiber diameter of 0.01 to 100 μm are used, and those in the form of fibers have a fiber diameter of 0.5 to 30 μm. Furthermore, these are grafted with organic titanates, aminosilane compounds, epoxysilane compounds, or the various monomers mentioned above, and the amount is generally 200 parts by weight, depending on the difference in their specific gravity.

Examples of the plasticizer include phosphoric acid ester, adipic acid ester, sepatic acid ester, azelaic acid ester, glycolic acid ester, trimellitic acid ester, and the like.

Flame retardants include phosphate esters, 7% rogene phosphate esters, various 10-gen substituted organic compounds, antimony dioxide, barium metaborate, zinc borate, titanium phosphate, tin oxide, calcium phosphite, and hypochlorite. Inorganic compounds such as calcium phosphate and red phosphorus; in addition to these, condensed phosphoric acid amides, fatty acid monoglyceride borate esters, etc. are exemplified.

Examples of blowing agents include evaporative blowing agents of organic solvents, inorganic blowing agents such as ammonium bicarbonate, sodium bicarbonate, sodium borohydride, and water, and organic blowing agents such as azo-based, nitrone-based, and hydrazide-based blowing agents. .

Examples of antistatic agents include cationic activators such as primary alkylamine salts, tertiary alkylamine salts, and quaternary alkyl ammonium salts; monovalent metal salts of fatty acids, sulfuric esters of fatty alcohols/L[, fatty acid ethyl sulfonate,
Anion activators such as alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, succinic acid ester sulfonates, and phosphate ester salts; partial fatty acid esters of polyhydric alcohols such as polyoxypropylene glycerol esters, fatty alcohols Nonionic activators such as ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols; Examples include ethyl imidacillin sulfate, zinc methylstearyldithiocarbamate, and polyoxyethylene bisphenol A.

The copolymer composition of the present invention can be produced by any method depending on the method for producing the copolymer that is its constituent component. For example, it can be blended in the form of latex, suspension, solution, powder, beads, pellets, etc. Although these compositions can be molded directly, they are generally molded using a Banbury mixer, kneader, or single-screw or double-screw molding process.
A uniform composition can be obtained by kneading in a melt mixer such as a screw extruder.

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

The parts and percentages shown in the examples are as follows: 70 parts of pure water, 0.2 parts of potassium persulfate, and 0.2 parts of sodium dodecylbenzenesulfonate were placed in a 5e reactor equipped with a heavy stirrer and plate baffles. After charging and purging the inside of the reactor with nitrogen gas, the temperature was raised to 70° C. with stirring. The following monomer solution (containing t-dodecyl mercaptan) was added to this reactor.
(1) to (3) were successively added over 5 hours. Simultaneously with the start of addition of this monomer solution, the following emulsifier and polymerization initiator aqueous solutions were continuously added over 5 hours. after that,
The temperature was raised to 75°C and maintained for 2 hours to obtain latex with a polymerization rate of 98.7%. A calcium chloride aqueous solution was added to the obtained polymer latex to coagulate it, and the product was recovered.

Table 1 shows the analysis results during the polymerization process.

From elemental analysis of the product and mass balance during the polymerization process, it was confirmed that the obtained product was a copolymer composition with a wide composition distribution.

Acrylonitrile 20101 steel βυ 50
85 98 Total addition amount (part') 5
0 20 300 Emulsifier-polymerization initiator aqueous solution Pure water 5
0 parts Sodium dodecylbenzenesulfonate
1 part potassium persulfate
0.2 parts Polymerization Example-2 The reactor used in Polymerization Example-1 was charged with 70 parts of pure water, 0.2 parts of potassium persulfate, and 0.1 part of sodium lauryl sulfate, and the inside of the reactor was purged with nitrogen gas. Afterwards, it was heated with stirring, and when the internal temperature reached 65°C, 3 parts of a monomer solution consisting of 5 parts of N-phenylmaleimide, 8 parts of acrylonitrile, and 87 parts of styrene were added, and the mixture was heated to 70°C over 30 minutes. ℃
The temperature rose to . Next, the remaining monomer solution (97 parts), 0.1 part of potassium persulfate, and 1 part of sodium lauryl sulfate were added.
and 50 parts of pure water were continuously added over 5 hours. Note that t-dodecyl mercaptan was used as a chain transfer agent.

Thereafter, the temperature was raised to 75°C and held for 2 hours, and the polymerization rate was 98.
A 6% latex was obtained. This latex was coagulated with an aqueous calcium chloride solution, and the product was recovered.

From elemental analysis of the product and mass balance during the polymerization process, it was confirmed that the obtained product did not contain a copolymer with a total content of N-phenylmaleimide and acrylonitrile of 7% or less.

Polymerization Example 3 According to the polymerization method of Polymerization Example 1, a mixed solution consisting of 1 part of N-phenylmaleimide, 2 parts of acrylonitrile, and 97 parts of styrene was polymerized to obtain a product with a polymerization rate of 98.2%.

From the elemental analysis of the product and the material balance that can be determined during the polymerization process, the obtained product is a copolymer consisting only of a copolymer with a total content of N-phenylmaleimide and acrylonitrile of 7% by weight or less. This was confirmed.

Polymerization Example-4 70 parts of pure water, 0.05 part of potassium persulfate, and potassium alkenylsuccinate were added to the reactor used in Polymerization Example-1.
@111-1@1lIIIlllo was charged, and the pH of the aqueous phase was adjusted to 7.2 with an aqueous potassium dihydrogen phosphate-sodium hydrogen carbonate solution. Next, the inside of the reactor was purged with nitrogen gas, and then the temperature was raised to 70° C. while stirring. A mixed solution consisting of 30 parts of N-phenylmaleimide, 20 parts of acrylonitrile, 50 parts of styrene and 0.3 parts of t-dotesyl mercaptan, as well as 0.2 parts of potassium persulfate and 1-■ alkenylsuccinic acid were added to the reactor. An aqueous solution consisting of 1 part of potassium potassium and 50 parts of pure water was continuously added over 5 hours.

Thereafter, the temperature was raised to 75°C and held for 2 hours, and the polymerization rate was 98.
A 7% latex was obtained. During the polymerization, a potassium dihydrogen phosphate-sodium hydrogen carbonate aqueous solution was added to adjust the pH of the aqueous phase to 7.1 to 7.3. The obtained latex was coagulated with an aqueous calcium chloride solution, and the product was collected.

From the elemental analysis of the product and the mass balance during the polymerization process, it was found that the obtained product contained less than 7% by weight of N-phenylmaleimide. It was confirmed that a certain copolymer was not included.

Polymerization Example-5 Into the reactor used in Polymerization Example-1, 70 parts of pure water, 0.1 part of potassium persulfate, 0.2 part of potassium alkenylsuccinate, and 0.05 part of sodium lauryl sulfate were charged, and dihydrogen phosphate was added. The pH of the aqueous phase was adjusted to 67 with an aqueous solution of potassium-dissulfur hydrogen phosphate. Next, the inside of the reactor was purged with nitrogen gas, and then the temperature was raised to 70°C while stirring. A mixed solution consisting of 12 parts of N-phenylmaleimide and 8 parts of acrylonitrile and 80 parts of styrene were added to this while increasing the styrene ratio in the monomers added (mixed solution/styrene: 40/60 at the beginning of addition). After the end,
Mixed solution/styrene: O/100) was added continuously over 5 hours.

In addition, at the same time as starting addition of this monomer, potassium persulfate
．． An aqueous solution consisting of 2 parts of potassium alkenylsuccinate, 0.8 parts of potassium alkenylsuccinate, 0.4 parts of sodium lauryl sulfate, and 50 parts of pure water was continuously added over 5 hours. Thereafter, the mixture was heated to 75° C. and maintained for 3 hours to obtain latex with a polymerization rate of 98.5%. During the polymerization, a potassium dihydrogen phosphate-sodium hydrogen phosphate aqueous solution was added to adjust the pH of the aqueous phase to 6.5 to 6.9. The obtained latex was coagulated with an aqueous calcium chloride solution, and the product was collected. Table 2 shows the analysis results during the polymerization process.

From elemental analysis of the product and mass balance during the polymerization process, it was confirmed that the obtained product was a copolymer composition with a wide composition distribution.

Polymerization Example-6 Into the reactor used in Polymerization Example-1, 80 parts of pure water, 0.1 part of potassium persulfate, 0.3 part of potassium alkenylsuccinate, and 0.8 part of sodium dodecylbenzenesulfonate were charged, and phosphoric acid The pH of the aqueous phase was adjusted to 7.2 by adding potassium dihydrogen-sodium hydroxide aqueous solution. Next, the inside of the reactor was replaced with nitrogen gas, and then the temperature was raised to 70° C. while stirring.

After adding 15 parts of a solution consisting of 9 parts of N-phenylmaleimide, 14 parts of acrylonitrile, 70 parts of α-methylstyrene, and 0.4 parts of t-dodecylmercaptan, the temperature was raised to 75°C over 80 minutes. . Then, the remaining monomer solution (78 parts) and potassium persulfate 0.2
1 part, potassium alkenylsuccinate 0.5 part, sodium dodecylbenzenesulfonate 0.5 part and pure water 60 parts were continuously added over 6 hours. Then,
1 part N-phenylmaleimide and acrylonitrile) IJle 6
of the solution was added continuously over 1 hour. After that, 75℃
The temperature was raised to 1 and maintained for 3 hours to obtain a latex with a polymerization rate of 98.7%.

During the polymerization, a potassium dihydrogen phosphate-sodium hydroxide aqueous solution was added to adjust the pH of the aqueous phase to 7.2 to 7.5. An aqueous magnesium sulfate solution was added to the obtained latex to coagulate it, and the product was recovered.

From elemental analysis of the product and mass balance during the polymerization process, it was confirmed that the obtained product did not contain a copolymer with a total content of N-phenylmaleimide and acrylonitrile of 7% by weight or less. Ta.

Polymerization Example-7 The reactor used in Polymerization Example-1 was charged with 60 parts of pure water, 0.1 part of potassium persulfate, and 0.2 part of sodium dodecylbenzenesulfonate, and after purging the inside of the reactor with nitrogen gas, the mixture was stirred. The temperature was then raised to 70°C. Add 20% methacrylic acid to this
and 80 parts of styrene, while increasing the styrene ratio in the monomers added (methacrylic acid/styrene: 40/60 at the beginning of addition → methacrylic acid/styrene: O/100 at the end of addition) over 6 hours. It was added continuously. Note that t-dodecyl mercaptan was used as a chain transfer agent. Simultaneously with the start of monomer addition, an aqueous solution consisting of 0.3 parts of potassium persulfate, 1.2 parts of sodium dodecylbenzenesulfonate, and 60 parts of pure water was continuously added over 6 hours. Thereafter, the temperature was raised to 75°C and maintained for 3 hours to obtain latex with a polymerization rate of 99.2%. The obtained latex was coagulated with an aqueous calcium chloride solution, and the product was collected. From the polymerization process mass balance, it was confirmed that the obtained product was a copolymer composition having a wide composition distribution.

Polymerization Example-8 A maleic anhydride-styrene copolymer with a uniform composition was synthesized by a known solution polymerization method (based on Japanese Patent Publication No. 60-45642) using methyl ethyl ketone as a solvent and benzoyl peroxide as a polymerization initiator. .

Polymerization Example-9 By a known solution polymerization method, using toluene as a solvent and benzoyl peroxide as a polymerization initiator, the intrinsic viscosity was 0.47 dll/? (Chloroform solution, 30
The following monomer solutions (11 to (3)) were substantially polymerized in the presence of 50 parts of poly(2°6-dimethylphenylene-1,4-ether) (measured value at °C). The product was obtained by sequentially adding each time the solution was completed.

Acrylonitrile 20 5 l
Steel [608598 total addition amount (mol% content)
A mixture of 50 parts of a copolymer (intrinsic viscosity: 0.47), 5 parts of N-phenylmaleimide O, 0.5 parts of acrylonitrile, and 49 parts of styrene was polymerized to obtain a product.

From elemental analysis of the product and mass balance during the polymerization process, the obtained product (2,6-xylenol (!: 2-8
Exclude copolymer of e6-drimethylphenol. ) was confirmed to be a copolymer consisting only of a copolymer with a total content of N-phenylmaleimide and acrylonitrile of 7% or less.

Polymerization Examples 11 to 12 After synthesizing a maleic anhydride-styrene copolymer using methyl ethyl ketone as a solvent and benzoyl peroxide as a polymerization initiator in accordance with a known solution polymerization method (Japanese Patent Publication No. 6O-45642). , and imidized with aniline to obtain an N-phenylmaleimide-styrene copolymer with a uniform composition.

Polymerization Example 13 80 parts of acrylonitrile and 70 parts of styrene were copolymerized by a known suspension polymerization method (based on Japanese Patent Publication No. 49-87590) to obtain a copolymer with an intrinsic viscosity of 0.61 d (1/y).

Table 4 shows the analysis results of product-1-18 obtained above. Here, the composition of the copolymer was determined from elemental analysis of C1H, N and O, and mass balance during the polymerization process.

In addition, the content of monomers (~, (B-2) and (B-3) in total of 7% or less was determined from the above elemental analysis values and mass balance in the polymerization process. The intrinsic viscosity, [η], is a value measured in a dimethylformamide solution at 30°C.

In addition, the abbreviations in each table are as follows: NPMI
: N-phenylmaleimide 8N : acrylonitrile MAA : methacrylic acid MAH : maleic anhydride MMA : methyl methacrylate S : styrene AMS : α-methylstyrene PPE : poly(2,6-dimethylphenylene-l,
4-ether) Examples 1 to 4 and Comparative Examples 1 to 3 Polymerization Examples 2 to 5. Copolymers (compositions) obtained in 9 to 12 were used alone or by mixing them in the ratios shown in Table 5. 30.1 parts of triethylene glycol-bis(8-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate) and 0 parts of dilauryl-8,3/-thiodipropionate as stabilizers per 100 parts of the composition. .1 part and 0.2 part of H(2,4-sheet t-7' tylphenyl) pentaerythritol diphosphite and 0.1 part of ethylene bisstearamide were added to the vented container.
Kneaded at 250 to 300°C while devolatilizing in a shaft extruder,
Pelleted.

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

This pellet was molded using an injection molding machine at 25 ON3[)°C to prepare a test piece, and its physical properties were measured.

The results are shown in Table 5.

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

Izot impact strength with O-notch (abbreviated as NI): 1/4
Inch thickness test piece, measured value at 23°C.

0 Heat Distortion Temperature (abbreviated as HDT): Value measured on a L/4 inch thick specimen, 264 psi load, without annealing.

O Solvent Resistance: After the test piece was immersed in gasoline at 80°C for 24 hours, the condition of the surface roughness etc. was observed with the naked eye.

Examples 5 to 6 A copolymer composition consisting of the copolymers (compositions) obtained in Polymerization Examples 1 and 6 to 8 was coated with glass fibers (surface-treated with an aminosilane compound, about 7 μm in diameter, about 6 in length). A composition containing 20% glass fiber was obtained.

A test piece was prepared according to the method of the above example, and its physical properties were measured. Table 6 shows the composition and measurement results of the copolymer composition.

Comparative Example 4 Using the copolymer obtained in Polymerization Example 13, a composition containing 20% glass fiber was obtained in the same manner as in Example 5, and its physical properties were measured. The composition and measurement results are shown in Table 6.

<Effects of the Invention> The copolymer composition of the present invention has excellent heat resistance, chemical resistance, mechanical properties, etc., and has very good affinity with various organic and inorganic materials.

Therefore, vehicle parts, ship parts, aircraft parts, electrical and electronic parts, building materials, office equipment, power tools, agricultural machinery parts, household goods, and sports and leisure products that require heat resistance, chemical resistance, and mechanical properties. It can be widely used in many fields such as supplies.

Claims (1)

[Claims] Any of the maleimide monomer (A-1) and the unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic resin and/or a rubbery polymer. 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 these A composition consisting of a copolymer obtained by polymerizing a monomer (C) copolymerizable with and having an average composition (excluding thermoplastic resin and rubbery polymer) of the formula ( 1) and (
2), and the total content of the monomers (A), (B-2) and (B-3) is 7.
A copolymer composition characterized in that it consists of 1 to 70% by weight of copolymer (1) and 99 to 30% by weight of copolymer (2) of more than 7% by weight. 〇Copolymer (A)/[(A)+(B)+(C)]×100=1-6
0% by weight--(1) (C)/[(A)+(B)+(C)]×100=0-5
0% by weight --(2)