Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
  • C08F212/10—Styrene with nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/42—Nitriles
  • C08F220/44—Acrylonitrile
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
  • B29K2025/04—Polymers of styrene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3055—Cars
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

• ABS resin Acrylonitrile-butadiene-styrene copolymer resin
• OA equipment Acrylonitrile-butadiene-styrene copolymer resin
• housing materials such as automobile interior materials
• heat-resistant imparting materials for example, Patent Documents 1 and 2.
• the ABS resin containing the maleimide-based copolymer has a drawback of low chemical resistance, and in order to overcome this, a maleimide-based copolymer in which a vinyl cyanide monomer is copolymerized has been proposed.
• a maleimide-based copolymer in which a vinyl cyanide monomer is copolymerized has been proposed.
• Patent Document 3 and Patent Document 4 While the currently proposed copolymer obtained by copolymerizing a vinyl cyanide monomer has high heat resistance, there is a desire to further improve the fluidity.
• An object of the present invention is to provide a maleimide-based copolymer and a method for producing the same, which can obtain a resin composition having excellent fluidity while maintaining a balance between chemical resistance, heat resistance imparting property, and impact resistance.
• maleimide-based copolymer and ABS resin acrylonitrile-styrene-acrylic rubber copolymer resin (ASA resin), acrylonitrile-ethylene / propylene rubber-styrene copolymer resin (AES resin) or styrene-acrylonitrile copolymer resin (AES resin)
• the viscosity of the resin composition can be lowered without increasing the amount added to the resin composition. It was possible, and it was thought that it would contribute to speeding up molding and improving productivity.
• the present invention has the following gist.
• the maleimide according to (1) which has 40 to 59.5% by mass of an aromatic vinyl monomer unit, 5 to 20% by mass of a vinyl cyanide monomer unit, and 35 to 50% by mass of a maleimide monomer unit.
• the initial polymerization step of mixing and initiating the copolymerization, the remaining 50 to 90% by mass of the aromatic vinyl monomer, and the remaining total amount of the unsaturated dicarboxylic acid anhydride monomer are added separately or continuously, respectively.
• It has a final polymerization step of obtaining a polymer and an imidization step of imidizing the dicarboxylic acid anhydride monomer unit of the obtained copolymer to a maleimide monomer unit using ammonia or a primary amine.
• the method for producing a maleimide-based copolymer according to any one of 1) to (4). (6) One or more selected from 5 to 40% by mass of the maleimide-based copolymer according to any one of (1) to (4) and ABS resin, ASA resin, AES resin or SAN resin. Resin composition having 60 to 95% by mass of the resin of. (7) An injection-molded article using the resin composition according to (6). (8) The injection-molded article according to (7), which is used as an interior member or an exterior member of an automobile.
• a maleimide-based copolymer and a method for producing the same can be obtained, which can obtain a resin composition having excellent fluidity while maintaining a balance between chemical resistance, heat resistance imparting property, and impact resistance. Further, chemical resistance, heat resistance, and impact resistance obtained by kneading and mixing a maleimide-based copolymer with one or more resins selected from ABS resin, ASA resin, AES resin, and SAN resin. A resin composition having an excellent balance of physical properties and high fluidity can be obtained.
• the maleimide-based copolymer of the present invention has an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a maleimide monomer unit.
• the aromatic vinyl monomer that can be used in the maleimide-based copolymer is used to improve the hue of the resin composition, and is used, for example, styrene, o-methylstyrene, m-methylstyrene, p-methyl.
• styrene 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene.
• styrene which has a high effect of improving hue, is preferable.
• the aromatic vinyl monomer may be used alone or in combination of two or more.
• the amount of the aromatic vinyl monomer unit contained in the maleimide-based copolymer is preferably 40 to 59.5% by mass, more preferably 45 to 55% by mass. Specifically, for example, it is 40, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 59.5 mass%, and is between any two of the numerical values exemplified here. It may be within the range.
• the hue of the resin composition obtained by setting the amount of the aromatic vinyl monomer unit to 40% by mass or more does not become yellowish, and the hue of the resin composition obtained by setting the amount to 59.5% by mass or less does not become yellowish. Heat resistance can be improved.
• the vinyl cyanide monomer that can be used in the maleimide-based copolymer is used to improve the chemical resistance of the resin composition, and examples thereof include acrylonitrile, methacrylonitrile, etacrylonitrile, and fumaronitrile. .. Among these, acrylonitrile, which has a high effect of improving chemical resistance, is preferable.
• the vinyl cyanide monomer may be used alone or in combination of two or more.
• the amount of the vinyl cyanide monomer unit contained in the maleimide-based copolymer is preferably 5 to 20% by mass, more preferably 7 to 15% by mass. Specifically, for example, it is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20% by mass, and is within the range between any two of the numerical values exemplified here. You may.
• the amount of the vinyl cyanide monomer unit is 5% by mass or more, the chemical resistance of the obtained resin composition is improved, and when the amount is 20% by mass or less, the hue of the obtained resin composition becomes yellowish. It does not take on.
• Maleimide monomers that can be used for maleimide-based copolymers are used to improve the heat resistance of the resin composition, and are, for example, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and the like. There are N-alkylmaleimide, and N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. Among these, N-phenylmaleimide, which has a high effect of improving heat resistance, is preferable.
• the maleimide monomer may be used alone or in combination of two or more.
• an aromatic vinyl monomer, a vinyl cyanide monomer and a maleimide monomer may be copolymerized.
• the anhydride monomer unit may be imidized with ammonia or a primary amine.
• the amount of the maleimide monomer unit contained in the maleimide-based copolymer is preferably 35 to 50% by mass, more preferably 37 to 45% by mass. Specifically, for example, it is 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50% by mass, and any of the numerical values exemplified here. It may be within the range between the two.
• the heat resistance of the maleimide-based copolymer obtained by setting the amount of the maleimide monomer unit to 35% by mass is improved, and the impact strength of the maleimide-based copolymer obtained by setting the amount to 50% by mass or less does not decrease. ..
• the maleimide-based copolymer may contain a dicarboxylic acid anhydride monomer unit having an effect of improving the compatibility between the maleimide-based copolymer and other resins.
• a dicarboxylic acid anhydride monomer unit In order to introduce a dicarboxylic acid anhydride monomer unit into a maleimide-based copolymer, an unsaturated dicarboxylic acid anhydride monomer is copolymerized with the above-mentioned monomer, or the above-mentioned aromatic vinyl monomer is used.
• the imidization ratio should be adjusted so that the dicarboxylic acid anhydride monomer unit remains.
• the unsaturated dicarboxylic acid anhydride monomer include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. Among these, it is preferable to use maleic anhydride, which has a high effect of improving compatibility.
• the unsaturated dicarboxylic acid anhydride monomer may be used alone, but two or more kinds may be used in combination.
• the amount of the dicarboxylic acid anhydride monomer unit contained in the maleimide-based copolymer is preferably 0.5 to 10% by mass, more preferably 0.1 to 2% by mass. Specifically, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1. It is 2,1.3,1.4,1.5,2,3,4,5,6,7,8,9,10% by mass, and is within the range between any two of the numerical values exemplified here. It may be.
• the compatibility between the maleimide-based copolymer obtained by setting the amount of the dicarboxylic acid anhydride monomer unit to 0.5% by mass or more and the resin such as ABS is improved, and it is obtained by setting the amount to 10% by mass or less.
• the thermal stability of the resulting resin composition is improved.
• the maleimide-based copolymer is a copolymerizable monomer other than an aromatic vinyl monomer, a vinyl cyanide monomer, a maleimide monomer, and an unsaturated dicarboxylic acid anhydride monomer, as an effect of the present invention. May be copolymerized as long as it does not inhibit the above.
• the monomers copolymerizable with the maleimide-based copolymer include, for example, acrylic acid ester monomers such as methylacrylic acid ester, ethylacrylic acid ester, and butylacrylic acid ester, methylmethacrylic acid ester, and ethylacrylic acid ester.
• methacrylic acid ester monomer acrylic acid
• vinylcarboxylic acid monomer such as methacrylic acid, acrylic acid amide and methacrylic acid amide.
• the monomer copolymerizable with the maleimide-based copolymer may be used alone or in combination of two or more.
• the amount of residual maleimide monomer contained in the maleimide-based copolymer is preferably less than 300 ppm, more preferably less than 230 ppm, still more preferably less than 200 ppm. By setting the amount of the residual maleimide monomer to less than 300 ppm, the hue of the obtained resin composition is further improved.
• the amount of residual maleimide monomer is a value measured under the conditions described below.
• Device name Gas chromatograph GC-2010 (manufactured by Shimadzu Corporation)
• the temperature rise analysis is performed at a column temperature of 80 ° C.
• the glass transition temperature of the maleimide-based copolymer is 165 ° C. to 200 ° C., preferably 170 ° C. to 200 ° C., in that it efficiently improves the heat resistance of the resin to be kneaded and mixed, such as ABS resin and ASA resin. , More preferably 175 ° C to 185 ° C. Specifically, for example, it is 165, 170, 175, 176, 177, 178, 179, 180, 185, 190, 195, 200 ° C., and is within the range between any two of the numerical values exemplified here. May be good.
• the glass transition temperature is a value measured by DSC and is a measured value under the measurement conditions described below. Device name: Differential scanning calorimeter Robot DSC6200 (manufactured by Seiko Instruments Inc.) Heating rate: 10 ° C / min
• the melt mass flow rate of the maleimide-based copolymer is a value measured under the conditions of 265 ° C. and 98 N load measured by the method described in JIS K 7210, and is 25 to 80 g / 10 minutes. Specifically, for example, it is 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80 g / 10 minutes, and any two of the numerical values exemplified here. It may be within the range between the two. If it is less than 25 g / 10 minutes, the fluidity of the mixed resin is lowered, and if it exceeds 80 g / 10 minutes, the impact resistance is lowered.
• the maleimide-based copolymer To lower the melt mass flow rate of the maleimide-based copolymer, increase the content of the dicarboxylic acid anhydride monomer unit contained in the maleimide-based copolymer, or use other monomers that lower the melt mass flow rate. It may be polymerized.
• the polymerization method of the maleimide-based copolymer includes, for example, solution polymerization, bulk polymerization and the like.
• Solution polymerization is preferable from the viewpoint that a maleimide-based copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing addition or the like.
• the solvent for solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to form and has little adverse effect.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone, tetrahydrofuran and 1,4-dioxane.
• Ethers such as benzene, toluene, xylene, chlorobenzene and other aromatic hydrocarbons, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, etc., at the time of volatilization recovery of maleimide-based copolymers
• Methyl ethyl ketone and methyl isobutyl ketone are preferable because of the ease of solvent removal.
• any of continuous polymerization type, batch type (batch type) and semi-batch type can be applied.
• the method for producing the maleimide-based copolymer is not particularly limited, but it can be preferably obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150 ° C.
• the polymerization initiator is not particularly limited, but for example, known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and Benoxyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2- Known organic peroxides such as ethyl hexanoate, di-t-butyl peroxide, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy
• One type or a combination of two or more types may be used. From the viewpoint of controlling the reaction rate of polymerization and the polymerization rate, it is preferable to use an azo compound or an organic peroxide having a 10-hour half-life of 70 to 120 ° C.
• the amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass, based on 100% by mass of all the monomer units. It is 1.0% by mass.
• the weight average molecular weight of the maleimide-based copolymer is 50,000 to 300,000, preferably 50,000 to 200,000. Specifically, for example, it is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 300,000, and the numerical values exemplified here. It may be within the range between any two of. If the weight average molecular weight is 50,000 or less, the impact resistance is lowered, and if it exceeds 300,000, the fluidity is lowered.
• a chain transfer agent can be used in the production of the maleimide-based copolymer.
• the chain transfer agent used is not particularly limited, and examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, and turpinolene. is there.
• the amount of the chain transfer agent used is not particularly limited as long as a maleimide-based copolymer having a target weight average molecular weight can be obtained, but is not particularly limited, but is based on 100% by mass of all the monomers to be copolymerized.
• It is preferably 0.01 to 0.8% by mass, and more preferably 0.1 to 0.5% by mass.
• amount of the chain transfer agent used is 0.01% by mass to 0.8% by mass, a maleimide-based copolymer having a target weight average molecular weight can be easily obtained.
• a method of introducing a maleimide monomer unit into a maleimide-based copolymer a method of copolymerizing a maleimide monomer with another monomer (direct method) or an unsaturated dicarboxylic acid anhydride monomer is used.
• Aromatic vinyl monomer and vinyl cyanide monomer are copolymerized in advance, and the dicarboxylic acid anhydride monomer unit in the copolymer is further imidized with ammonia or a primary amine to make a maleimide.
• post-imidization method There is a method of converting to a monomer unit (post-imidization method). The post-imidization method is preferable because the amount of residual maleimide monomer in the copolymer is small.
• the primary amine is, for example, an alkyl such as methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine and decylamine.
• alkyl such as methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine and decylamine.
• amines and aromatic amines such as chlor or brom-substituted alkylamines, aniline, toluidine, and naphthylamines, of which aniline and cyclohexylamines are preferred.
• These primary amines may be used alone or in combination
• the amount of the primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalents, more preferably 0.85 to 1.05, relative to the dicarboxylic acid anhydride monomer unit. It is a molar equivalent. When it is 0.7 molar equivalent or more with respect to the dicarboxylic acid anhydride monomer unit in the maleimide-based copolymer, the thermal stability is good, which is preferable. Further, when it is 1.1 molar equivalents or less, the amount of primary amine remaining in the maleimide-based copolymer is reduced, which is preferable.
• the reaction between ammonia or the primary amine and the dicarboxylic acid anhydride monomer unit in the copolymer particularly from the dicarboxylic acid anhydride monomer unit to maleimide.
• a catalyst can be used as needed for the purpose of improving the dehydration ring closure reaction.
• the type of catalyst is not particularly limited, but for example, a tertiary amine can be used.
• the tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, and N-diethylaniline.
• the amount of the tertiary amine added is not particularly limited, but is preferably 0.01 molar equivalent or more with respect to the dicarboxylic acid anhydride monomer unit.
• the temperature of the imidization reaction in the present invention is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. When the temperature of the imidization reaction is 100 ° C. or higher, the reaction rate is sufficiently high, which is preferable from the viewpoint of productivity. When the temperature of the imidization reaction is 250 ° C. or lower, deterioration of physical properties due to thermal deterioration of the maleimide-based copolymer can be suppressed, which is preferable.
• Initial polymerization step Total amount of vinyl cyanide monomer charged, 10 to 90% by mass of aromatic vinyl monomer, 0 to 30% by mass of unsaturated dicarboxylic acid anhydride monomer
• Medium-term polymerization step of mixing and starting the copolymerization at the initial stage of polymerization The balance of the amount of the aromatic vinyl monomer charged and the rest of the amount of the unsaturated dicarboxylic acid anhydride monomer are divided or continuously, respectively.
• Final polymerization step 1/10 or more of the amount of the aromatic vinyl monomer divided or continuously added after the total amount of the unsaturated dicarboxylic acid anhydride monomer has been charged.
• the obtained copolymer having an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a dicarboxylic acid anhydride monomer unit is imide with ammonia or a primary amine.
• a method for removing volatile components such as a solvent used for solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide-based copolymer or a solution after completion of post-imidization is known.
• Method can be adopted.
• a vacuum devolatilization tank with a heater or a devolatilization extruder with a vent can be used.
• the devolatile, molten maleimide-based copolymer is transferred to the granulation process, extruded into strands from a porous die, and processed into pellets by a cold cut method, an aerial hot cut method, or an underwater hot cut method. Can be done.
• the maleimide-based copolymer thus obtained can be used as a heat-resistant imparting agent for the obtained resin composition by kneading and mixing with various resins.
• the various resins are not particularly limited, but include ABS resin, ASA resin, AES resin, and SAN resin. Since the maleimide-based copolymer and these resins have excellent compatibility, a high heat resistance-imparting effect can be obtained.
• the blending ratio of the maleimide-based copolymer and these resins is one or more selected from the group consisting of 5 to 40% by mass of the maleimide-based copolymer, ABS resin, ASA resin, AES resin and SAN resin.
• the resin content is preferably 60 to 95% by mass, more preferably 10 to 30% by mass of the maleimide copolymer, one or two selected from the group consisting of ABS resin, ASA resin, AES resin and SAN resin.
• the above resin is 70 to 90% by mass.
• the method for kneading and mixing the maleimide-based copolymer and various resins is not particularly limited, but a known melt-kneading technique can be used. Screws such as a single-screw extruder, a fully meshing unidirectional rotating twin-screw extruder, a fully meshing different-direction rotating twin-screw extruder, and a non- or incompletely meshing twin-screw extruder can be preferably used.
• the resin composition Since the resin composition has excellent fluidity, it is suitable for use in injection molded products.
• injection moldings include televisions, copying machines, telephones, watches, refrigerators, vacuum cleaners, air conditioners, washing machines, PCs, DVD / Blu-ray players, audio systems, dryers, keyboards, tablets, digital cameras, attache cases, pachinko machines, etc.
• maleimide-based copolymer (A-1) 20 parts by mass of styrene, 10 parts by mass of acrylonitrile, 5 parts by mass of maleic anhydride, 0.1 parts by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.6 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-5) 20 parts by mass of styrene, 10 parts by mass of acrylonitrile, 5 parts by mass of maleic anhydride, 0.1 parts by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.8 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-6) 20 parts by mass of styrene, 10 parts by mass of acrylonitrile, 5 parts by mass of maleic anhydride, 0.1 parts by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.11 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-8) 20 parts by mass of styrene, 15 parts by mass of acrylonitrile, 5 parts by mass of maleic anhydride, 0.1 parts by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.6 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and was measured under the following conditions.
• Device name SYSTEM-21Shodex (manufactured by Showa Denko KK) Column: 3 PLgelMIXED-B in series Temperature: 40 ° C Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL).
• melt mass flow rate MFR
• the melt mass flow rate was measured at 265 ° C. and a load of 98 N in accordance with JIS K 7210.
• Glass-transition temperature As for the glass transition temperature, the midpoint glass transition temperature (Tmg) of the maleimide copolymer was measured according to JIS K-7121 with the following equipment and measurement conditions.
• Amount of residual maleimide monomer Dissolve 0.5 g of the sample in 5 ml of a 1,2-dichloroethane solution (0.014 g / L) containing undecane (internal standard substance). Then, 5 ml of n-hexane is added and shaken with a shaker for 10 to 15 minutes to precipitate. Only the supernatant is injected into the gas chromatograph with the polymer precipitated. From the peak area of the obtained maleimide monomer, a quantitative value was calculated using a coefficient obtained from the internal standard substance.
• Examples 1 to 8 and Comparative Examples 1 to 6 (kneading and mixing of a maleimide-based copolymer and ABS resin)
• Maleimide-based copolymers A-1 to A-8 and B-1 to B-6 which are commercially available maleimide-based copolymers having no vinyl cyanide monomer unit, "MS-NIP” ( (Denka Co., Ltd.) and ABS resin "GR-3000” (Denka Co., Ltd.) or ASA resin "Luran S 757G” (manufactured by INEOS Polymer Co., Ltd.) were blended in the blending ratios shown in Tables 3 and 4.
• test piece was measured by the 50 method (load 50 N, heating rate 50 ° C./hour) using a test piece of 10 mm ⁇ 10 mm and a thickness of 4 mm.
• load 50 N load 50 N
• heating rate 50 ° C./hour heating rate 50 ° C./hour
• test piece 10 mm ⁇ 10 mm and a thickness of 4 mm.
• an HDT & VSPT test device manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
• a crack was observed at 23 ° C. after 48 hours by a 1/4 ellipsoid method having a test piece shape of 316 ⁇ 20 ⁇ 2 mm, a semi-major axis of 250 mm, and a semi-minor axis of 150 mm.
• the test piece was manufactured by press-molding pellets at 260 ° C. and cutting out to eliminate the influence of molding strain.
• the chemical was carried out using toluene.
• the critical strain was calculated by the following formula.
• the maleimide-based copolymers A-1 to A-8 of the present invention have a weight average molecular weight without reducing the content of maleimide monomer units in the composition as in Examples 1 to 8.
• a high glass transition temperature and a high melt mass flow rate were realized by lowering.
• the weight average molecular weight was lowered by a certain amount or more, the heat resistance and the chemical resistance were lowered as in Comparative Example 5 and Comparative Example 6.
• the maleimide-based copolymers B-1 to B-6 that do not fall within the scope of the present invention are outside the scope of the present invention, and Comparative Examples 1 to 1 to which these maleimide-based copolymers and ABS resin are kneaded and mixed.
• the resin composition of Comparative Example 6 was inferior in any of impact resistance, fluidity, heat resistance, and chemical resistance.
• the maleimide-based copolymer of the present invention has an excellent balance of chemical resistance, heat resistance, impact resistance, and fluidity by being mixed and mixed with compatible ABS resin, ASA resin, AES resin, and SAN resin. Since the resin composition can be obtained and the fluidity of the mixed resin can be increased, the molding speed and the production speed can be improved.

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