CN117222678A - Crosslinkable acrylic copolymer, composition containing acrylic copolymer and rubber material - Google Patents

Crosslinkable acrylic copolymer, composition containing acrylic copolymer and rubber material Download PDF

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Publication number
CN117222678A
CN117222678A CN202280023231.7A CN202280023231A CN117222678A CN 117222678 A CN117222678 A CN 117222678A CN 202280023231 A CN202280023231 A CN 202280023231A CN 117222678 A CN117222678 A CN 117222678A
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Prior art keywords
acrylic copolymer
mass
structural unit
derived
acrylate
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冈田凉
大盐真穗
北川纪树
内藤雅嗣
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Osaka Soda Co Ltd
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Osaka Soda Co Ltd
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    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • 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
    • C08F224/00—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 heterocyclic ring containing oxygen
    • 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
    • C08F24/00—Homopolymers and 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 heterocyclic ring containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L37/00—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 heterocyclic ring containing oxygen; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a rubber material which has excellent solidification property and excellent scorch stability at the initial stage without reducing compression set resistance. The present invention relates to an acrylic copolymer containing 50 to 99.5 mass% of a structural unit (A) derived from an alkyl acrylate and/or a structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond, and 0.5 to 20 mass% of a structural unit (A); a composition comprising the above acrylic copolymer and a crosslinking agent; a rubber material is prepared from the composition.

Description

Crosslinkable acrylic copolymer, composition containing acrylic copolymer and rubber material
Technical Field
The present invention relates to an acrylic copolymer and a rubber material thereof, and more particularly, to a composition containing an acrylic copolymer which is an acrylic copolymer excellent in coagulability and which is used for providing a rubber material excellent in compression set resistance and stability (scorch stability) against initial vulcanization.
Background
In general, an acrylic polymer is a polymer mainly composed of acrylic acid ester, and is known as a material excellent in various physical properties related to durability, and is widely used as an industrial rubber material for engine gaskets, oil hoses, air hoses, O-rings, etc., or an automobile rubber material.
In order to use the polymer as such a member, rubber elasticity is imparted by crosslinking, and for this purpose, about 1 to 5 mass% of a reactive crosslinking group monomer is copolymerized in the acrylic copolymer.
As examples of the crosslinking group monomer, a structural unit derived from an unsaturated monomer having a halogen group (for example, a chlorine group or the like), a structural unit derived from an unsaturated monomer having a carboxyl group, a structural unit derived from an unsaturated monomer having an epoxy group, or the like can be exemplified.
In view of such a situation, patent document 1 discloses an acrylic rubber composition excellent in tensile strength and compression set resistance and having electrical insulation properties, and a sulfide thereof, and a hose member, a sealing member, and a vibration-damping rubber member using the same, by using an alkyl butene diacid as a carboxyl group-containing crosslinkable monomer. However, the normal physical properties such as strength TB and elongation EB and the compression set resistance are not satisfactory.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-257319
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide a composition containing an acrylic copolymer which is an acrylic copolymer excellent in coagulability, and which is used for providing a rubber material excellent in compression set resistance and scorch stability.
Solution for solving the problem
The present inventors have made various studies and as a result, have found that the object can be achieved by an acrylic copolymer comprising 50 to 99.5% by mass of a structural unit (a) derived from an alkyl acrylate and/or a structural unit (a) derived from an alkoxyalkyl acrylate and 0.5 to 20% by mass of a structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond, a composition comprising the acrylic copolymer and a crosslinking agent, and a rubber material produced from the composition.
The mode of the invention is as follows.
An acrylic copolymer comprising 50 to 99.5% by mass of a structural unit (A) derived from an alkyl acrylate and/or a structural unit (A) derived from an alkoxyalkyl acrylate, and 0.5 to 20% by mass of a structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the following general formula (1).
(in the general formula (1), R 1 The copolymerizable double bond is any of vinyl and allyl. )
The acrylic copolymer according to item 1, wherein the structural unit (B) derived from the succinic anhydride-structure-containing monomer having a copolymerizable double bond represented by the above general formula (1) is a structural unit derived from allyl succinic anhydride.
The acrylic copolymer according to any one of items 1 or 2, which contains 0.5 to 49.5% by mass of a structural unit (C) derived from an alkyl methacrylate having an alkyl group having 1 to 16 carbon atoms.
An acrylic copolymer-containing composition according to item 4, which contains the acrylic copolymer according to any one of items 1 to 3 and a crosslinking agent.
Item 5 is a rubber material produced from the acrylic copolymer-containing composition of item 4.
ADVANTAGEOUS EFFECTS OF INVENTION
The acrylic copolymer of the present invention is excellent in coagulability, and a rubber material produced from a composition containing the acrylic copolymer is excellent in compression set resistance and scorch stability, and therefore is suitable as a rubber material for automobiles such as a fuel system hose or an air system hose, a gasket or a gasket as a duct material or a sealing material.
Detailed Description
< acrylic copolymer >
First, the acrylic copolymer in the present invention will be described. The acrylic copolymer of the present invention contains 50 to 99.5% by mass of a structural unit (A) derived from an alkyl acrylate and/or a structural unit (A) derived from an alkoxyalkyl acrylate, and 0.5 to 20% by mass of a structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond.
Among the structural units derived from an alkyl acrylate and/or the structural units (a) derived from an alkoxyalkyl acrylate, the structural units derived from an alkyl acrylate having an alkyl group of 1 to 12 carbon atoms and/or the structural units derived from an alkoxyalkyl acrylate having an alkoxyalkyl group of 2 to 8 carbon atoms are preferable, the structural units derived from an alkyl acrylate having an alkyl group of 2 to 6 carbon atoms and/or the structural units derived from an alkoxyalkyl acrylate having an alkoxyalkyl group of 2 to 6 carbon atoms are more preferable, and the structural units derived from an alkyl acrylate having an alkyl group of 2 to 4 carbon atoms and/or the structural units derived from an alkoxyalkyl acrylate having an alkoxyalkyl group of 2 to 4 carbon atoms are more preferable. Among the structural units derived from alkyl acrylate and the structural units derived from alkoxyalkyl acrylate, the structural units derived from alkyl acrylate are preferable. The structural unit (a) may be a structural unit derived from a single compound or may be a structural unit derived from 2 or more compounds.
Specific examples of the structural unit derived from an alkyl acrylate having an alkyl group having 1 to 12 carbon atoms include structural units derived from an acrylic ester such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-dodecyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate, and structural units derived from ethyl acrylate and n-butyl acrylate are preferable. They may be used alone or may be structural units derived from 2 or more alkyl acrylates.
Specific examples of the structural unit derived from an acrylic acid ester having an alkoxyalkyl group having 2 to 8 carbon atoms include structural units derived from acrylic acid esters such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, 2-ethoxyethyl acrylate, 2-propoxyethyl acrylate, 2-butoxyethyl acrylate, 2-methoxypropyl acrylate, 2-ethoxypropyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 4-methoxybutyl acrylate, and 4-ethoxybutyl acrylate, and structural units derived from methoxyethyl acrylate are preferable. They may be used alone or may be structural units derived from at least 2 alkoxyalkyl acrylates.
The content of the structural unit derived from an alkyl acrylate and/or the structural unit (a) derived from an alkoxyalkyl acrylate in the acrylic copolymer of the present invention is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, most preferably 80% by mass or more, still more preferably 85% by mass or more, and the upper limit is preferably 99.5% by mass or less, more preferably 99% by mass or less, particularly preferably 98.5% by mass or less, of the total structural units of the acrylic copolymer. When the structural unit (a) is in the above range, it is preferable in terms of cold resistance and oil resistance.
In the present specification, when a plurality of structural units (a) are contained, the content of the structural units (a) refers to the total content. The same applies to other structural units.
The structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond is a structural unit derived from a compound represented by the following general formula (1). The structural unit (B) may be a structural unit derived from a single compound or may be a structural unit derived from 2 or more compounds.
(in the general formula (1), R 1 The copolymerizable double bond is any of vinyl and allyl. )
In the structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the general formula (1), R in the general formula (1) 1 Preferably, the vinyl group is a vinyl group or an allyl group, and more preferably an allyl group.
Specific examples of the structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the general formula (1) include allyl succinic anhydride and vinyl succinic anhydride. These monomer units having a succinic anhydride structure and having a copolymerizable double bond may be used alone or in combination of two or more. Among them, allyl succinic anhydride is preferable.
The content of the structural unit (B) derived from the succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the general formula (1) in the acrylic copolymer of the present invention is preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 2 mass% or more, and the upper limit is preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, and particularly preferably 7 mass% or less, based on the total structural units of the acrylic copolymer.
In the acrylic copolymer of the present invention, the total amount of the structural unit (a) derived from an alkyl acrylate and/or the structural unit (a) derived from an alkoxyalkyl acrylate and the structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the general formula (1) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, of the total structural units of the acrylic copolymer. In addition, it may be substantially 100 mass%.
The acrylic copolymer of the present invention may contain a structural unit (C) derived from an alkyl methacrylate, preferably a structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 16 carbon atoms, more preferably a structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, and particularly preferably a structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms. The structural unit (C) may be a structural unit derived from a single compound or may be a structural unit derived from 2 or more compounds.
Examples of the structural unit derived from an alkyl methacrylate having an alkyl group having 1 to 16 carbon atoms include structural units derived from an alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, n-lauryl methacrylate, and n-octadecyl methacrylate. They may be used alone or as structural units derived from more than 2 alkyl methacrylates.
The content of the structural unit (C) derived from the alkyl methacrylate in the acrylic copolymer of the present invention may be 0% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or 3% by mass or more, based on the total structural units of the acrylic copolymer. The upper limit may be 49.5 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less. When the structural unit (C) derived from the alkyl methacrylate is in the above range, it is preferable in terms of heat resistance, oil resistance and cold resistance.
In the acrylic copolymer of the present invention, the total amount of the structural unit (a) derived from an alkyl acrylate and/or the structural unit (a) derived from an alkoxyalkyl acrylate, the structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the general formula (1), and the structural unit (C) derived from an alkyl methacrylate is preferably 85 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more, of the total structural units of the acrylic copolymer. In addition, it may be substantially 100 mass%.
In addition to the structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond, the acrylic copolymer of the present invention may contain a crosslinking group monomer which is generally used in combination. As the crosslinking group monomer generally used herein, a structural unit derived from an unsaturated monomer having a carboxyl group can be exemplified. The structural unit derived from an unsaturated monomer having a carboxyl group may be a structural unit derived from a single compound or may be a structural unit derived from 2 or more compounds.
Examples of the unsaturated monomer having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, 2-pentenoic acid and cinnamic acid, unsaturated dicarboxylic acids such as fumaric acid, maleic acid and itaconic acid, monomethyl fumarate, monoethyl fumarate, mono-n-butyl fumarate, monomethyl maleate, monoethyl maleate, mono-2-ethylhexyl maleate and mono-n-butyl maleate; a butenedioic acid monocycloalkyl ester such as monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, etc.; monoesters of itaconic acid such as monomethyl itaconate, monoethyl itaconate, mono-n-butyl itaconate, and monocyclohexyl itaconate; etc. Examples thereof include monoesters of unsaturated dicarboxylic acids such as monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monoethyl itaconate, monopropyl itaconate and monobutyl itaconate.
The content of the structural unit derived from the unsaturated monomer having a carboxyl group in the acrylic copolymer of the present invention may be 0 to 10% by mass, may be 0 to 7% by mass, and may be 0 to 5% by mass of the total structural units of the acrylic copolymer.
Furthermore, the acrylic copolymer of the present invention may contain, in addition to the above-mentioned structural units, structural units derived from other monomers copolymerizable with these. Examples of the other structural unit include a structural unit derived from a monomer having a structure containing an N-substituted maleimide, a structural unit derived from an ethylenically unsaturated nitrile, a structural unit derived from a (meth) acrylamide monomer, a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a conjugated diene monomer, a structural unit derived from a non-conjugated diene, a structural unit derived from another olefin, and the like. These structural units may be structural units derived from a single compound or structural units derived from 2 or more compounds.
Examples of the structural unit derived from a monomer having a structure containing N-substituted maleimide include structural units derived from compounds such as N- (4-anilinophenyl) maleimide and hydroxyphenylmaleimide.
Examples of the structural unit derived from an ethylenically unsaturated nitrile include structural units derived from a compound such as acrylonitrile, methacrylonitrile, α -methoxyacrylonitrile, dicyanoethylene, and the like.
As the structural unit derived from the (meth) acrylamide-based monomer, examples thereof include those derived from acrylamide, methacrylamide, diacetone acrylamide, diacetone methacrylamide, N-butoxymethylacrylamide, N-butoxyethylacrylamide N-butoxyethyl methacrylamide, N-methoxymethyl methacrylamide, N-propoxymethyl methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, structural units of compounds such as N-dimethylacrylamide, N-diethylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, ethylacrylamide, crotonamide, cinnamamide, maleic diamide, itaconic diamide, methylmaleimide, methyl-clothes Kang Xianan, maleimide, and itaconic imide.
Examples of the structural unit derived from an aromatic vinyl monomer include structural units derived from a compound such as styrene, α -methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α -fluorostyrene, p-trifluoromethylstyrene, p-methoxystyrene, p-aminostyrene, p-dimethylaminostyrene, p-acetoxystyrene, styrenesulfonic acid or a salt thereof, α -vinylnaphthalene, 1-vinylnaphthalene-4-sulfonic acid or a salt thereof, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine, divinylbenzene, diisopropenylbenzene, and vinylbenzyl chloride.
Examples of the structural unit derived from the conjugated diene monomer include structural units derived from compounds such as 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2-chloro-1, 3-butadiene, 1, 2-dichloro-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 2-neopentyl-1, 3-butadiene, 2-bromo-1, 3-butadiene, 2-cyano-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, chloroprene, and piperylene.
Examples of the structural unit derived from a non-conjugated diene include structural units derived from a non-conjugated diene compound such as 1, 4-pentadiene, 1, 4-hexadiene, ethylidene norbornene, norbornadiene, dicyclopentadiene, and the like.
Examples of the structural unit derived from another olefin monomer include structural units derived from esters such as dicyclopentadiene acrylate, dicyclopentadiene methacrylate, dicyclopentadiene ethyl acrylate and dicyclopentadiene ethyl methacrylate, and compounds such as ethylene, propylene, vinyl chloride, vinylidene chloride, 1, 2-dichloroethylene, vinyl acetate, vinyl fluoride, vinylidene fluoride, 1, 2-difluoroethylene, vinyl bromide, vinylidene bromide, 1, 2-dibromoethylene, ethyl vinyl ether and butyl vinyl ether.
In the case where the acrylic copolymer of the present invention contains structural units derived from these other copolymerizable monomers, the content of the total structural units may be 0 to 15% by mass, 0 to 10% by mass, or 0 to 5% by mass.
The content of the structural unit in the acrylic copolymer of the present invention can be determined by nuclear magnetic resonance spectroscopy of the resulting polymer.
Regarding the molecular weight range of the acrylic copolymer in the present invention, the Mooney viscosity (ML) at 100℃in the Mooney scorch test defined in JIS K6300 is used in terms of processability 1+4 ) The molecular weight is preferably in the range of 10 to 100, more preferably in the range of 15 to 90, and even more preferably in the range of 20 to 80.
< method for producing acrylic copolymer >
The acrylic copolymer used in the present invention can be obtained by polymerizing various monomers, respectively. The monomers used may be commercially available ones, and are not particularly limited.
The polymerization reaction mode may be any of emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization, but from the viewpoint of ease of control of the polymerization reaction, it is preferable to use emulsion polymerization at normal pressure, which is generally used as a conventionally known method for producing an acrylic copolymer.
In the case of polymerization by emulsion polymerization, a conventional method may be used, and conventionally known polymerization initiators, emulsifiers, chain transfer agents, polymerization inhibitors and the like which are generally used may be used.
The emulsifier used in the present invention is not particularly limited, and nonionic emulsifiers and anionic emulsifiers generally used in emulsion polymerization methods can be used. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alcohol ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, and examples of the anionic emulsifier include alkylbenzenesulfonate, alkyl sulfate salt, polyoxyethylene alkyl ether sulfate salt, polyoxyalkylene alkyl ether phosphate or its salt, and fatty acid salt, and 1 or 2 or more of these may be used.
The amount of the emulsifier used in the present invention may be any amount generally used in emulsion polymerization. Specifically, the amount of the monomer to be charged is preferably in the range of 0.01 to 10 mass%, more preferably 0.03 mass% or more, still more preferably 0.05 mass% or more, still more preferably 7 mass% or less, still more preferably 5 mass% or less. In the case of using a reactive surfactant as a monomer component, the addition of an emulsifier is not necessarily required.
The polymerization initiator used in the present invention is not particularly limited, and a polymerization initiator generally used in emulsion polymerization can be used. As a specific example thereof, examples thereof include inorganic polymerization initiators represented by persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, 2-bis (4, 4-bis (t-butylperoxy) cyclohexyl) propane, 1-bis (t-butylperoxy) cyclohexane, 1-bis (t-butylperoxy) cyclohexane, n-butyl 4, 4-bis (t-butylperoxy) valerate, 2-bis (t-butylperoxy) butane, t-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1, 3-tetramethylbutyl hydroperoxide, t-butylperoxy cumene, di-t-butyl peroxide, di-t-hexyl peroxide, di (2-t-butylperoxy isopropyl) benzene, dicumyl peroxide, p-menthane hydroperoxide, and the like diisobutyryl peroxide, bis (3, 5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, bis (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, cumyl peroxyneodecanoate, 1, 3-tetramethylbutyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoic acid peroxy) hexane, 1, 3-tetramethylbutyl peroxy-2-ethylhexanoic acid, t-hexyl peroxy (2-ethylhexanoic acid), t-butyl peroxy laurate, t-butyl peroxy (3, 5-trimethylhexanoate), t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane, t-butyl peroxyacetate organic peroxide polymerization initiators such as t-hexyl peroxybenzoate, t-butyl peroxybenzoate, 2, 5-dimethyl-2, 5-bis (t-butyl peroxybenzoate), hydrogen peroxide, azobisisobutyronitrile, 4' -azobis (4-cyanovaleric acid), 2' -azobis [2- (2-imidazolin-2-yl) propane, 2' -azobis (propane-2-carboxamidine), 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamide, 2' -azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl ] propane }, azo initiators such as 2,2 '-azobis (1-imino-1-pyrrolidine-2-methylpropane) and 2,2' -azobis { 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide }. These polymerization initiators may be used in an amount of 1 or in combination of 2 or more.
The amount of the polymerization initiator used in the present invention may be an amount generally used in emulsion polymerization. Specifically, the amount of the monomer to be charged is preferably 0.01 to 5% by mass, more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more, still more preferably 4% by mass or less, still more preferably 3% by mass or less.
Further, the organic peroxide and the inorganic peroxide as the polymerization initiator can be used as redox-type polymerization initiators by combining them with a reducing agent. The reducing agent used in combination is not particularly limited, and examples thereof include compounds containing a metal ion in a reduced state such as ferrous sulfate and cuprous naphthenate, methane compounds such as sodium methanesulfonate, amine compounds such as dimethylaniline, and inorganic salts having reducing properties such as ascorbic acid and its salts, and alkali metal salts of sulfurous acid and thiosulfate. These reducing agents may be used alone or in combination of 2 or more. The amount of the reducing agent to be used is preferably 0.0003 to 10.0 parts by mass based on 100 parts by mass of the monomer to be charged.
Chain transfer agents may be used as desired. Specific examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-stearyl mercaptan, vinyl ethers such as 2, 4-diphenyl-4-methyl-1-pentene, 2, 4-diphenyl-4-methyl-2-pentene, dimethyl xanthate disulfide, xanthogenic compounds such as diisopropyl xanthate disulfide, thiuram compounds such as terpinolene, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, and tetramethyl thiuram monosulfide, phenol compounds such as 2, 6-di-t-butyl-4-methylphenol, and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbons such as methylene chloride, dibromomethane, and carbon tetrabromide, halogenated hydrocarbons such as α -benzyloxy styrene, α -benzyloxy acrylonitrile, vinyl ethers such as α -benzyl acrylamide, triphenylethane, pentachenyl ethane, acrolein, methacrolein, mercaptoacetic acid, thiomalic acid, and mercaptoacetic acid 2-ethylhexyl ester, and the like, and 1 or 2 may be used. The amount of these chain transfer agents is not particularly limited, and is usually 0 to 5 parts by mass based on 100 parts by mass of the charged monomer.
Examples of the polymerization inhibitor include hydroxylamine, hydroxylamine sulfate, diethylhydroxylamine, hydroxylamine sulfonic acid and alkali metal salts thereof, quinone compounds such as sodium dimethyldithiocarbamate and hydroquinone, and the like. The amount of the polymerization inhibitor is not particularly limited, and is usually 0 to 2 parts by mass based on 100 parts by mass of the total monomers.
Further, the polymer obtained according to the above method can be adjusted in pH by using a base as a pH adjuster as needed. Specific examples of the base include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, inorganic ammonium compounds, organic amine compounds, and the like. The pH is preferably in the range of pH1 to 11, more preferably pH1.5 or more, still more preferably pH2 or more, still more preferably pH10.5 or less, still more preferably pH10 or less.
In addition, a polymer auxiliary material such as a particle diameter regulator, a chelating agent, an oxygen scavenger, or the like may be used as needed.
The emulsion polymerization may be carried out in any of batch, semi-batch, and continuous modes. The polymerization time and polymerization temperature are not particularly limited. The polymerization initiator may be appropriately selected depending on the kind of the polymerization initiator used, but is usually used at a polymerization temperature of 10 to 100℃for a polymerization time of 0.5 to 100 hours.
The method for recovering the polymer obtained by the above method is not particularly limited, and a method which is generally carried out may be employed. As an example of the method, the following method can be given: the polymerization liquid is continuously or intermittently supplied to the aqueous solution containing the coagulant, and by this operation, a coagulated slurry is obtained. In this case, the temperature of the aqueous solution containing the coagulant is affected by the type and amount of the monomer, and the coagulation conditions such as shearing force caused by stirring, etc., and therefore, the temperature is not limited to a specific value, but is usually 50℃or higher, preferably in the range of 60℃to 100 ℃.
Not limited to the production of the acrylic copolymer of the present invention, the coagulability of the emulsion polymerization liquid containing the acrylic copolymer is important in production, and in the case of adding the emulsion polymerization liquid dropwise to the coagulation liquid, if the emulsion polymerization liquid is an emulsion polymerization liquid having good coagulability, the coagulation starts immediately after the dropwise addition, and the above-mentioned effects are obtained. On the other hand, in the case of an emulsion polymerization liquid having poor coagulability, the emulsion does not coagulate immediately after the dropping, and the emulsion concentration in the coagulated liquid increases, so that the torque of the stirrer increases. Further, if the emulsion is rapidly solidified in a state where the emulsion concentration in the tank is high, there is a concern that not only the safety accompanying the torque increase but also the size of the solidified chips becomes large, and the insufficiently solidified emulsion remains in the chips, resulting in a decrease in the yield. In view of the above, in order to ensure safety and a sufficient yield, it is necessary to reduce the stirring speed, and as a result, the solidification time becomes long, and the productivity is lowered.
The coagulated slurry obtained by the above method is preferably subjected to water washing to remove the coagulant. If the washing with water is not performed or the washing is insufficient, there is a concern that ion residues derived from the coagulant may precipitate in the molding step.
The acrylic copolymer can be obtained by removing water from the coagulated slurry after washing with water and drying. The drying method is not particularly limited, and generally, a flash dryer, a flow dryer, or the like is used for drying. In addition, a dehydration step using a centrifuge or the like may be performed before the drying step.
< composition containing acrylic copolymer >
The acrylic copolymer-containing composition of the present invention contains at least the above acrylic copolymer and a crosslinking agent.
As the crosslinking agent, conventionally known crosslinking agents generally used for crosslinking rubbers such as polyamine compounds, polyepoxide compounds, polyisocyanate compounds, and aziridine compounds can be used. Among them, a polyamine compound can be suitably used.
Examples of the polyamine compound include hexamethylenediamine, hexamethylenediamine carbamate, and N, aliphatic polyamine compounds such as N '-bis-cinnamaldehyde-1, 6-hexamethylenediamine, 4' -methylenedianiline, m-phenylenediamine, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4'- (m-phenylenediisopropylene) diphenylamine, 4' - (p-phenylenediisopropylene) diphenylamine, 4 '-bis (. Alpha., aromatic polyamine compounds such as α -dimethylbenzyl) diphenylamine, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 4 '-diaminoanilide, 4' -bis (4-aminophenoxy) biphenyl, m-xylylenediamine, p-xylylenediamine, 1,3, 5-trimellitamide, 1,3, 5-triaminomethylbenzene, and isophthalic dihydrazide.
Examples of the polyvalent epoxy compound include glycidyl ether type epoxy compounds such as phenol novolac type epoxy compounds, cresol type epoxy compounds, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, brominated bisphenol a type epoxy compounds, brominated bisphenol F type epoxy compounds, hydrogenated bisphenol a type epoxy compounds, and the like; alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds, and other polyvalent epoxy compounds.
Examples of the polyvalent isocyanate compound include 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, 1,3, 6-hexamethylene triisocyanate, 1,6, 11-undecyl triisocyanate and bicycloheptane triisocyanate.
Examples of the aziridine compound include tris-2, 4,6- (1-aziridinyl) -1,3, 5-triazine, tris [1- (2-methyl) aziridinyl ] phosphine oxide, and hexa [1- (2-methyl) aziridinyl ] triphosphazene.
These crosslinking agents may be used alone or in combination of 2 or more. The amount of the crosslinking agent is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, preferably 20 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2.5 parts by mass or less, based on 100 parts by mass of the acrylic copolymer of the present invention.
The acrylic copolymer-containing composition of the present invention may be optionally blended with other additives commonly used in the art, such as lubricants, softeners, antioxidants, light stabilizers, fillers, reinforcing agents, plasticizers, processing aids, pigments, colorants, crosslinking accelerators, crosslinking aids, crosslinking retarders, antistatic agents, foaming agents, and the like. These may be used alone or in combination of 2 or more.
Examples of the softener include lubricating oil, process oil, coal tar, castor oil, stearic acid, and calcium stearate.
Examples of the antioxidant include amines such as amines, phosphates, quinolines, cresols, phenols, and metal dithiocarbamates, and amines such as diphenylamine derivatives and phenylenediamine derivatives are preferable.
Examples of the crosslinking accelerator include guanidine compounds, amine compounds, thiourea compounds, thiazole compounds, sulfenamide compounds, thiuram compounds, and quaternary ammonium salts, and guanidine compounds and amine compounds are preferable, and guanidine compounds are more preferable.
Examples of the guanidine compound include 1, 3-diphenylguanidine and 1, 3-di-o-tolylguanidine.
Examples of the amine compound include secondary amine compounds such as dimethylamine, diethylamine, dipropylamine, diallylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-sec-butylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di-undecylamine, didodecyl amine, ditridecyl amine, ditetradecyl amine, ditpentadecyl amine, ditetradecyl amine, di-2-ethylhexyl amine, dioctadecyl amine, tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, triallylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, tri-sec-butylamine, trihexylamine, triheptylamine, trioctylamine, trisnonylamine, tridecyl amine, tri-undecyl amine, and tri-dodecyl amine.
Further, the rubber, resin, etc. which are generally used in this technical field may be blended within a range not departing from the gist of the present invention. Examples of the rubber used in the present invention include butadiene rubber, styrene-butadiene rubber, isoprene rubber, natural rubber, nitrile rubber, acrylonitrile-butadiene-isoprene rubber, acrylic rubber, ethylene-propylene-diene rubber, and chlorohydrin rubber, and examples of the resin include PMMA (polymethyl methacrylate) resin, PS (polystyrene) resin, PUR (polyurethane) resin, PVC (polyvinyl chloride) resin, EVA (ethylene/vinyl acetate) resin, AS (styrene/acrylonitrile) resin, and PE (polyethylene) resin. These may be used alone or in combination of 2 or more.
The total amount of the rubber and the resin to be blended is 50 parts by mass or less, preferably 10 parts by mass or less, and more preferably 1 part by mass or less, based on 100 parts by mass of the acrylic copolymer of the present invention.
As a method for compounding the acrylic copolymer-containing composition of the present invention, any device used in the field of conventional polymer processing, for example, an open mill, a banbury mixer, various kneaders, and the like can be used.
The compounding step may be performed according to a general procedure performed in the field of polymer processing. For example, the method can be carried out according to the following steps: the polymer is kneaded only first, then, a compounding agent other than a crosslinking agent and a crosslinking accelerator is added to prepare an a kneaded compound, and then, a B kneading is performed in which a crosslinking agent and a crosslinking accelerator are added.
Rubber materials (specifically, crosslinked materials can be produced by heating to 100 to 250 ℃ C.) can be produced from the composition of the present invention. The crosslinking time varies depending on the temperature and is usually between 0.5 and 300 minutes. The crosslinking molding may be performed by heating the composition containing the acrylic copolymer to be molded before the molding, or by heating the composition to be molded before the molding to form a crosslinked product. As a specific method of the crosslinking molding, any method such as compression molding using a mold, injection molding, heating using a steam pot, an air bath, infrared rays, or microwaves can be used.
The acrylic copolymer of the present invention thus obtained is excellent in coagulability, and a rubber material produced from a composition containing the acrylic copolymer is excellent in compression set resistance and scorch stability.
Therefore, the rubber material of the present invention is suitably used as various gaskets such as O-rings, seals, separators, oil seals, shaft seals, bearing seals, mechanical seals, wellhead seals, seals for electric/electronic equipment, seals for air pressure equipment, cylinder head gaskets attached to a connecting portion between a cylinder block and a cylinder head, rocker cover gaskets attached to a connecting portion between a rocker cover and a cylinder head, oil pan gaskets attached to a connecting portion between an oil pan and a cylinder block or a transmission, gaskets for fuel cell separators attached between a pair of housings sandwiching a battery cell having a positive electrode, an electrolyte plate, and a negative electrode, gaskets for upper covers of hard disk drives, and various hoses such as extrusion molded products and mold crosslinked products used in automobiles around fuel tanks such as fuel hoses, filler neck hoses, ventilation hoses, vapor hoses, oil hoses, turbine air hoses, emission control hoses, etc., and various hoses such as radiator hoses, heater hoses, brake hoses, air conditioning hoses.
Examples
The present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to these examples. In examples and comparative examples, physical properties of the acrylic copolymer, the acrylic copolymer-containing composition containing the obtained acrylic copolymer and the crosslinking agent, and the rubber material produced using the acrylic copolymer-containing composition were evaluated as follows.
<Mooney viscosity (ML) of the Polymer 1+4 、100℃)>
For the acrylic copolymer, mooney viscosity was measured at a measurement temperature of 100℃using Mooney Viscometer AM-3 manufactured by Toyo Seiki Seisaku-Sho Co., ltd according to the Mooney viscosity test of the uncrosslinked rubber physical test method of JIS K6300 (ML 1+4 )。
< coagulability of acrylic copolymer >
Regarding the coagulability of the acrylic copolymer, 100 parts by mass of a coagulation liquid (2% magnesium sulfate aqueous solution) was heated to 80℃and 100 parts by mass of an emulsion polymerization liquid containing the acrylic copolymer was added dropwise while adjusting the dropping speed so as not to exceed 20% of the maximum torque of the stirrer, and the time required from the start of the dropping of the emulsion polymerization liquid to the coagulation of the entire amount was measured and evaluated. In this case, if the time until all the acrylic copolymer is coagulated is 5 minutes or less, the manufacturing process can be shortened or the amount of the coagulant can be reduced, and thus cost reduction can be achieved. In addition, since the amount of the coagulant can be reduced, the number of washing steps as a subsequent step can be reduced, which contributes to improvement of productivity.
< Mooney scorch time t5 (scorch stability) >
The acrylic copolymer composition was kneaded with a kneader and an open roll to prepare an uncrosslinked sheet having a thickness of 2 to 2.5mm, and the scorch stability was evaluated by measuring the time required to rise from the minimum Mooney viscosity by 5 points at 125℃using Mooney Viscometer AM-3 manufactured by Toyo Seisakusho Co., ltd. For the Mooney scorch test defined in JIS K6300.
< test of physical Properties in Normal state >
The acrylic copolymer composition was kneaded by a kneader and an open roll to prepare an uncrosslinked sheet having a thickness of 2 to 2.5mm, and the uncrosslinked sheet was subjected to a press treatment at 180℃for 10 minutes, and then heated by an air oven at 180℃for 3 hours to obtain a rubber material. Using the obtained crosslinked material, tensile test (strength TB, elongation EB) was evaluated by AGS-5KNY manufactured by Shimadzu corporation. The tensile test was carried out according to the method described in JIS K6251.
< compression set test >
The acrylic copolymer composition was kneaded by a kneader and an open roll to prepare an uncrosslinked sheet having a thickness of 2 to 2.5mm, and the uncrosslinked sheet was subjected to a press treatment at 180℃for 10 minutes to press a cylindrical test piece having a diameter of 29mm and a thickness of 12.5mm, and further heated by an air oven at 180℃for 3 hours to obtain a rubber material for test. Using the obtained crosslinked material, the compression set was calculated by releasing the compression after the test piece was compressed by 25% in accordance with the compression set test defined in JIS K6262 and left to stand at 175℃for 72 hours. The smaller the compression set means the smaller the compression set, the more excellent the compression set resistance.
Example 1
To a polymerization reactor equipped with a thermometer, a stirrer, a nitrogen inlet pipe and a pressure reducer, 200 parts by mass of water, 1.7 parts by mass of polyoxyalkylene alkyl ether phosphate, 48.5 parts by mass of ethyl acrylate as component (A), 48.5 parts by mass of n-butyl acrylate and 3.0 parts by mass of allyl succinic anhydride as component (B) were charged, deaeration under reduced pressure and nitrogen substitution were repeated, oxygen was sufficiently removed, then 0.1 part by mass of sodium ascorbate and 0.1 part by mass of potassium persulfate were added, emulsion polymerization was initiated at normal pressure and normal temperature, and the reaction was continued until the polymerization conversion rate reached 95%, and 0.0075 parts by mass of hydroquinone was added, to stop the polymerization. The emulsion polymerization solution obtained was coagulated with an aqueous magnesium sulfate solution, washed with water, and dried to obtain an acrylic copolymer a. The coagulability was evaluated by the method described above using a part of the emulsion polymerization solution obtained. The polymer mooney viscosity of the obtained acrylic copolymer a was evaluated in the manner described above.
The obtained acrylic copolymer and each compounding agent shown in Table 2 were kneaded A with a kneader at 120℃and further kneaded B with an open roll at room temperature to obtain an acrylic copolymer composition. The mooney scorch test of the obtained acrylic copolymer composition was evaluated in accordance with the above-described method. The results are shown in Table 2.
Further, the obtained acrylic copolymer composition was prepared into a rubber material by the above-described method, and the obtained crosslinked product was evaluated for its normal physical properties (strength TB, elongation EB) and compression set resistance. The results are shown in Table 2.
Example 2
An acrylic copolymer B was obtained in the same manner as in example 1, except that the amount of the charge monomer was changed to 46.1 parts by mass of ethyl acrylate, 46.1 parts by mass of n-butyl acrylate, and 3.0 parts by mass of allyl succinic anhydride, and 4.8 parts by mass of butyl methacrylate as the component (C) was added according to example 1. The physical properties of the acrylic copolymer composition using the obtained acrylic copolymer B and the rubber material obtained by crosslinking the acrylic copolymer composition were evaluated in the same manner as in example 1.
Comparative example 1
An acrylic copolymer C was obtained in the same manner as in example 1, except that the allyl succinic anhydride of the component (B) was changed to 3.0 parts by mass of monobutyl fumarate in accordance with example 1. The physical properties of the acrylic copolymer composition using the obtained acrylic copolymer C and the rubber material obtained by crosslinking the acrylic copolymer composition were evaluated in the same manner as in example 1.
Comparative example 2
An acrylic copolymer D was obtained in the same manner as in example 2, except that the allyl succinic anhydride of the component (B) was changed to 3.0 parts by mass of monobutyl fumarate in accordance with example 2. The physical properties of the acrylic copolymer composition using the obtained acrylic copolymer D and the rubber material obtained by crosslinking the acrylic copolymer composition were evaluated in the same manner as in example 1.
Comparative example 3
An acrylic copolymer E was obtained in the same manner as in example 1, except that 49.5 parts by mass of ethyl acrylate, 49.5 parts by mass of n-butyl acrylate and 1.0 part by mass of monobutyl fumarate were changed according to example 1. The physical properties of the acrylic copolymer composition using the obtained acrylic copolymer E and the rubber material obtained by crosslinking the acrylic copolymer composition were evaluated in the same manner as in example 1.
Comparative example 4
Polymerization was carried out in the same manner as in example 1 except that the allyl succinic anhydride of the component (B) was changed to 3.0 parts by mass of maleic anhydride according to example 1, but a large amount of aggregates were generated during the polymerization, and the polymerization was stopped. Therefore, each physical property cannot be evaluated.
TABLE 1
TABLE 2
As shown in table 1, examples 1 and 2, which are the acrylic copolymer of the present invention, were faster in solidification of emulsion and excellent in solidification property as compared with comparative examples 1, 2 and 3. In comparative example 4, maleic anhydride having a structure similar to that of allyl succinic anhydride was used, but it was considered that emulsion polymerization could not be performed because the solubility of maleic anhydride in water was too high. Further, as shown in Table 2, it was found that the rubber material produced from the composition containing the acrylic copolymer of the present invention was also excellent in scorch stability and compression set resistance. In comparative example 3 in which the amount of the crosslinking group monomer was reduced, the scorch stability was good, but the compression set resistance was greatly reduced.
Industrial applicability
The acrylic copolymer of the present invention can be widely used as a material for rubber products or resin products which use excellent setting properties, scorch stability and compression set resistance, or as an adhesive raw material or a paint raw material. In particular, the crosslinked product produced using the acrylic copolymer of the present invention is extremely effective for automotive applications such as fuel system hoses, air system hoses, duct materials, and the like.

Claims (5)

1. An acrylic copolymer comprising 50 to 99.5 mass% of a structural unit (A) derived from an alkyl acrylate and/or a structural unit (A) derived from an alkoxyalkyl acrylate, 0.5 to 20 mass% of a structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the following general formula (1),
in the general formula (1), R 1 The copolymerizable double bond is any of vinyl and allyl.
2. The acrylic copolymer according to claim 1, wherein the structural unit (B) derived from a succinic anhydride structure-containing monomer having a copolymerizable double bond represented by the general formula (1) is a structural unit derived from allyl succinic anhydride.
3. The acrylic copolymer according to any one of claims 1 or 2, which contains 0.5 to 49.5 mass% of the structural unit (C) derived from an alkyl methacrylate having an alkyl group having 1 to 16 carbon atoms.
4. An acrylic copolymer-containing composition comprising the acrylic copolymer according to any one of claims 1 to 3 and a crosslinking agent.
5. A rubber material made from the acrylic copolymer-containing composition according to claim 4.
CN202280023231.7A 2021-06-18 2022-03-28 Crosslinkable acrylic copolymer, composition containing acrylic copolymer and rubber material Pending CN117222678A (en)

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