WO2021071085A1 - Copolymère acrylique, procédé pour le fabriquer et composition de copolymère acrylique le comprenant - Google Patents

Copolymère acrylique, procédé pour le fabriquer et composition de copolymère acrylique le comprenant Download PDF

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WO2021071085A1
WO2021071085A1 PCT/KR2020/011183 KR2020011183W WO2021071085A1 WO 2021071085 A1 WO2021071085 A1 WO 2021071085A1 KR 2020011183 W KR2020011183 W KR 2020011183W WO 2021071085 A1 WO2021071085 A1 WO 2021071085A1
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monomer
weight
meth
acrylic copolymer
parts
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PCT/KR2020/011183
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English (en)
Korean (ko)
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정용석
한정수
이지영
여승욱
신상진
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주식회사 엘지화학
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Priority claimed from KR1020200094657A external-priority patent/KR102568623B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080006757.5A priority Critical patent/CN113195566B/zh
Priority to US17/311,891 priority patent/US20220025086A1/en
Priority to JP2021531646A priority patent/JP7160474B2/ja
Publication of WO2021071085A1 publication Critical patent/WO2021071085A1/fr

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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
    • 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
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy 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
    • 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
    • C08F222/10—Esters
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms

Definitions

  • the present invention relates to an acrylic copolymer, and more particularly, to an acrylic copolymer having excellent oil resistance and permanent compression reduction rate, a method for preparing the same, and an acrylic copolymer composition comprising the same.
  • Acrylic rubber is a polymer containing acrylic acid ester as a main component, and is known as rubber with excellent heat resistance, oil resistance and ozone resistance, and is widely used as a component material such as seals, hoses, tubes and belts in automobile related fields. Although a small amount of acrylic rubber is mainly used for important parts that influence the performance of automobiles, due to its characteristics, it is positioned as an important part such as parts that are applied to areas where vibration and noise occur, and parts that require heat resistance and oil resistance.
  • Acrylic rubber needs elasticity by crosslinking so that it can be used as a rubber part, and it must have excellent heat resistance and oil resistance under high temperature.
  • BACKGROUND ART In recent years, there is a demand for improvement in the performance of rubber parts due to the high output of the internal combustion engine, exhaust gas, etc., where the thermal environmental conditions around the internal combustion engine are severe, and the engine oil proceeds under high temperature conditions.
  • Crosslinkable acrylic rubber used for various purposes as described above requires excellent oil resistance and elasticity, which is a certain level of rubber properties.
  • high crosslinking density of acrylic rubber is required in order to realize durability suitable for the above use.
  • the object to be solved in the present invention is to provide an acrylic copolymer composition having excellent oil resistance and low permanent compression reduction ratio in order to solve the problems mentioned in the technology behind the background of the present invention.
  • the present invention includes a repeating unit derived from a main monomer and a part derived from a polyfunctional monomer, and the repeating unit derived from the main monomer is a repeating unit derived from a (meth)acrylic acid alkyl ester monomer , (Meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit and a crosslinkable monomer-derived repeating unit, wherein the polyfunctional monomer includes a vinyl group or an allyl group, and the polyfunctional monomer-derived portion is a total of 100 repeating units derived from the main monomer. It provides an acrylic copolymer contained in an amount of 0.0005 to 1 part by weight based on parts by weight.
  • preparing a main monomer mixture comprising a (meth) acrylic acid alkyl ester monomer, a (meth) acrylic acid alkoxy alkyl ester monomer and a crosslinkable monomer; And adding a polyfunctional monomer to the main monomer mixture and polymerizing, wherein the polyfunctional monomer is added in an amount of 0.0005 to 1 part by weight based on the total 100 parts by weight of the main monomer mixture.
  • the acrylic copolymer including the multifunctional monomer according to the present invention has excellent oil resistance by improving the crosslinking density of the polymer and maintains elasticity, which is a characteristic of rubber, so that the permanent compression reduction rate is small.
  • the terms'derived repeating unit' and'derived part' may refer to a component, structure, or the substance itself originated from a substance, and as a specific example, the'derived repeating unit' is a monomer that is introduced during polymerization of a polymer. It may refer to a repeating unit formed in the polymer by participating in the polymerization reaction, and the'derived part' may refer to a chain transfer agent that is introduced during polymerization of the polymer to participate in the polymerization reaction to induce a chain transfer reaction of the polymer. .
  • the term'rubber' refers to a plastic material having elasticity, and may mean rubber, elastomer, or synthetic latex.
  • the term'copolymer' may mean including all copolymers formed by copolymerization of a comonomer, and as a specific example, it may mean including both a random copolymer and a block copolymer.
  • the acrylic copolymer according to the present invention may include a repeating unit derived from a main monomer and a portion derived from a polyfunctional monomer.
  • the repeating unit derived from the main monomer may include a repeating unit derived from a (meth)acrylic acid alkyl ester monomer, a repeating unit derived from a (meth)acrylic acid alkoxyalkyl ester monomer, and a repeating unit derived from a crosslinkable monomer. .
  • the repeating unit derived from the (meth)acrylic acid alkyl ester monomer is a component that serves to increase workability, heat resistance, and cold resistance in the final product by controlling the glass transition temperature in the acrylic copolymer.
  • It may be a (meth)acrylic acid alkyl ester monomer containing an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms may mean including a linear or cyclic alkyl group having 1 to 8 carbon atoms.
  • the (meth) acrylate alkyl ester monomer is (meth) acrylate methyl, (meth) acrylate ethyl, (meth) acrylate propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate iso Butyl, (meth)acrylic acid n-amyl, (meth)acrylic acid isoamyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid cyclohexyl, and the like.
  • the (meth)acrylic acid alkyl ester monomer may be used alone or in combination of two or more, and specific examples may be ethyl (meth)acrylate, n-butyl (meth)acrylate monomer, and the like.
  • the content of the repeating unit derived from the (meth)acrylic acid alkyl ester monomer in the repeating unit derived from the main monomer may be 60 wt% to 95 wt%, 75 wt% to 93 wt%, or 80 wt% to 90 wt%, and this Within the range, there is an effect of excellent workability, heat resistance, and cold resistance of the acrylic copolymer according to the present invention.
  • the repeating unit derived from the (meth)acrylic acid alkoxyalkyl ester monomer is a component that controls the glass transition temperature in the acrylic copolymer to increase workability, heat resistance, and cold resistance in the final product, and is an alkoxyalkyl group having 1 to 8 carbon atoms. It may mean a (meth) acrylic acid alkyl ester monomer containing.
  • the (meth)acrylic acid alkoxyalkyl ester monomer is (meth)acrylate methoxymethyl, (meth)acrylate ethoxymethyl, (meth)acrylate 2-ethoxyethyl, (meth)acrylate 2-butoxyethyl, ( Meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-propoxyethyl, (meth)acrylic acid 3-methoxypropyl, (meth)acrylic acid 4-methoxybutyl, and the like.
  • the (meth)acrylic acid alkoxy alkyl ester monomer may be (meth)acrylic acid 2-methoxyethyl.
  • the content of the repeating unit derived from the (meth)acrylic acid alkoxy alkyl ester monomer in the repeating unit derived from the main monomer may be 1% by weight to 35% by weight, 7% by weight to 25% by weight, or 10% by weight to 20% by weight, within this range, the acrylic copolymer according to the present invention has excellent workability and oil resistance.
  • the total content of the repeating unit derived from the (meth)acrylate alkyl ester monomer and the repeating unit derived from the (meth)acrylate alkoxyalkyl ester monomer contained in the repeating unit derived from the main monomer according to the present invention is 80% to 99.9% by weight, 85 It may be from% to 99.9% by weight or from 90% to 99.5% by weight, and within this range, the acrylic copolymer according to the present invention has excellent workability, cold resistance and heat resistance.
  • the repeating unit derived from the crosslinkable monomer is a component for imparting a crosslinkable functional group in the acrylic copolymer, and may be at least one selected from the group consisting of a butenedionic acid monoester monomer, an epoxy group-containing monomer, and a halogen-containing monomer.
  • the butenedionic acid monoester monomer may be a butenedionic acid, that is, a maleic acid monoester monomer or a fumaric acid monoester monomer obtained by reacting an alcohol with a carboxyl group of maleic acid or fumaric acid.
  • the maleic acid monoester monomer is a maleic acid monoalkyl ester monomer such as monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monopentyl maleate, monodecyl maleate; monocyclopentyl maleate, Monocyclohexyl maleate, monocycloheptyl maleate, monocyclooctyl maleate, monomethyl cyclohexyl maleate, mono-3,5-dimethylcyclohexyl maleate, monodicyclopentanyl maleate, monoisobornyl maleate, etc.
  • maleic acid monoalkyl ester monomer such as monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monopentyl maleate, monodecyl maleate; monocyclopentyl maleate, Monocyclohexyl maleate, monocycloheptyl maleate, monocyclooctyl
  • Maleic acid monocycloalkyl ester monomer Maleic acid monocycloalkenyl, such as maleic acid monocyclopentenyl, maleic acid monocyclohexenyl, maleic acid monocycloheptenyl, maleic acid monocyclooctenyl, maleic acid dicyclopentadienyl, etc. Ester monomers; Etc.
  • the fumaric acid monoester monomers include fumaric acid monoalkyl ester monomers such as fumaric acid monomethyl, fumaric acid monoethyl, fumaric acid monopropyl, fumaric acid monobutyl, fumaric acid monohexyl, fumaric acid monooctyl, etc.; fumaric acid monocyclopentyl, fumaric acid monocyclohexyl, fumaric acid monocyclo Fumaric acid monocycloalkyl ester monomers such as heptyl, fumaric acid monocyclooctyl, fumaric acid monomethyl cyclohexyl, fumaric acid mono-3,5-dimethylcyclohexyl, fumaric acid dicyclopentanyl, fumaric acid isobornyl, and other fumaric acid monocycloalkyl ester monomers; fumaric acid monocyclopentenyl, fumaric acid And fumaric acid monocycloalkenyl ester monomers such as mono
  • the epoxy group-containing monomer may be glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, and the like.
  • the epoxy group-containing monomer may be glycidyl (meth) acrylate, allyl glycidyl ether, or the like.
  • the halogen-containing monomer is vinyl chloroacetate, vinyl bromo acetate, allyl chloro acetate, vinyl chloro propionate, vinyl chloro butyrate, vinyl bromo butyrate, 2-chloro ethyl acrylate, 3-chloro propyl acrylate, 4- Chlorobutyl acrylate, 2-chloro ethyl methacrylate, 2-bromo ethyl acrylate, 2-iodine ethyl acrylate, 2-chloroethyl vinyl ether, chloro methyl vinyl ether, 4-chloro-2-butenyl acrylate, vinyl Benzyl chloride, 5-chloromethyl-2-norbornene, 5-chloroacetoxy methyl-2-norbornene, and the like.
  • the halogen-containing monomer may be vinyl chloroacetate, vinyl benzyl chloride, 2-chloro ethyl acrylate, 2-chloroeth
  • the content of the repeating unit derived from the crosslinkable monomer in the repeating unit derived from the main monomer may be 0.1 to 20% by weight, 0.1% to 15% by weight, or 0.5% to 10% by weight, and within this range, the acrylic type according to the present invention
  • the crosslinking density of the copolymer is high, mechanical properties are excellent, the elongation of the obtained crosslinked product is improved, and compression set is prevented.
  • the repeating unit derived from the main monomer is a repeating unit derived from the (meth)acrylic acid alkyl ester monomer, a repeating unit derived from a (meth)acrylic acid alkoxyalkyl ester monomer, and a repeating unit derived from a crosslinkable monomer, in addition to the repeating unit derived from the (meth)acrylate alkyl ester monomer. And a repeating unit derived from another monomer copolymerizable with a repeating unit derived from the (meth)acrylic acid alkoxyalkyl ester monomer.
  • the polyfunctional monomer-derived part is a component that induces crosslinking between monomers to increase the crosslinking density of the polymer when preparing an acrylic copolymer, and is derived from a crosslinking agent containing two or more vinyl groups and allyl groups.
  • polyfunctional monomers include allyl such as divinylbenzene, 1,4-divinyloxybutane, divinyl sulfone, diallylphthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate, etc.
  • the polyfunctional monomer may be used alone or in combination of two or more.
  • the polyfunctional monomer may be used alone or in combination of two or more.
  • the content of the polyfunctional monomer-derived part may be 0.0005 parts by weight to 1.0 parts by weight, 0.001 parts by weight to 0.8 parts by weight, or 0.001 parts by weight to 0.05 parts by weight, based on 100 parts by weight of the repeating unit derived from the main monomer.
  • the crosslinking density of the acrylic copolymer according to the present invention can be improved, and accordingly, the oil resistance is increased and the permanent compression reduction rate is lowered, while the acrylic copolymer is prevented from being excessively stiff, so that workability and processability are also improved. It has an excellent effect.
  • the weight average molecular weight of the acrylic copolymer may be 200,000 g/mol to 4,000,000 g/mol, 300,000 g/mol to 3,000,000 g/mol, or 500,000 g/mol to 2,500,000 g/mol, and within this range, the acrylic copolymer There is an effect of reducing manufacturing time and realizing excellent mechanical properties.
  • the pattern viscosity (ML1+4, 100° C.) of the acrylic copolymer may be 10 to 70, 20 to 60, or 25 to 50, and there is an effect of excellent workability within this range.
  • a method for producing an acrylic copolymer includes the steps of preparing a main monomer mixture comprising a (meth)acrylate alkyl ester monomer, a (meth)acrylate alkoxyalkyl ester monomer, and a crosslinkable monomer; And adding 0.0005 parts by weight to 1 part by weight of a polyfunctional monomer and polymerizing them based on 100 parts by weight of the total of the main monomer mixture.
  • the polyfunctional monomer may contain a crosslinking agent containing two or more vinyl groups and allyl groups.
  • the content of the polyfunctional monomer may be 0.0005 parts by weight to 1.0 parts by weight, 0.001 parts by weight to 0.8 parts by weight, or 0.001 parts by weight to 0.05 parts by weight, based on 100 parts by weight of the total main monomer mixture.
  • the crosslinking density of the acrylic copolymer according to the present invention can be improved, and accordingly, the oil resistance is increased and the permanent compression reduction rate is lowered, while the acrylic copolymer is prevented from being excessively stiff, so that workability and processability are also improved. It has an excellent effect.
  • the step of preparing the main monomer mixture may be a step of mixing a monomer constituting the main chain of the acrylic copolymer, and the type and content of the monomers forming the main monomer mixture are determined to form a repeating unit derived from the main monomer described above. It may be the same as the type and content of the monomer for.
  • the acrylic copolymer may be carried out using a method such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, etc., such as initiators, emulsifiers, polymerization terminators, ion exchange water, molecular weight modifiers, activators, redox catalysts, etc. It may be carried out by an emulsion polymerization method such as a batch type, a semi-batch type, or a continuous type by using an additive additionally.
  • a method such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, etc.
  • initiators such as initiators, emulsifiers, polymerization terminators, ion exchange water, molecular weight modifiers, activators, redox catalysts, etc. It may be carried out by an emulsion polymerization method such as a batch type, a semi-batch type, or a continuous type by using an additive additionally.
  • the initiator examples include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; Diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide , Organic peroxides such as octanoyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutylate; And nitrogen compounds such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isobutyric acid (butyric acid)
  • an organic peroxide or inorganic peroxide initiator can be used as a redox polymerization initiator in combination with a reducing agent.
  • a reducing agent A compound containing metal ions in a reduced state, such as ferrous sulfate and cuprous naphthenate; sulfonic acid compounds such as sodium methanesulfonate; amine compounds such as dimethylaniline; and the like.
  • These reducing agents can be used alone or in combination of two or more.
  • the reducing agent may be used in an amount of 0.005 parts by weight to 20 parts by weight based on 1 part by weight of the peroxide.
  • the emulsifier may be selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers, and specific examples include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, poly Nonionic emulsifiers such as oxyethylene sorbitan alkyl esters; salts of fatty acids such as myristoic acid, palmitic acid, oleic acid and linolenic acid, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, higher alcohol sulfate ester salts, alkyl sulfo Anionic emulsifiers such as succinate; Cationic emulsifiers such as alkyl trimethyl ammonium chloride, dialkyl ammonium chloride, and benzyl ammonium chloride; Sulfo esters of ⁇ , ⁇ -un
  • Water may be used as the ion-exchanged water, and the ion-exchanged water may be used in an amount of 100 parts by weight to 400 parts by weight based on 100 parts by weight of the main monomer mixture.
  • the molecular weight modifier examples include mercaptans such as a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; And sulfur-containing compounds such as tetraethyl diuram disulfide, dipentamethylene diuram disulfide, and diisopropylxanthogen disulfide.
  • the molecular weight modifier may be used in an amount of 0.1 parts by weight to 3 parts by weight based on 100 parts by weight of the main monomer mixture.
  • the activator may be one or more selected from sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium linolenic acid, and sodium sulfate.
  • the activator may be used in an amount of 0.01 parts by weight to 0.15 parts by weight based on 100 parts by weight of the main monomer mixture.
  • the redox catalyst may be, for example, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediaminetetraacetate, and second copper sulfate.
  • the redox catalyst may be used in an amount of 0.01 parts by weight to 0.1 parts by weight based on 100 parts by weight of the main monomer mixture.
  • the acrylic copolymer composition according to the present invention may include the acrylic copolymer and filler obtained as described above.
  • the filler may be carbon black, silica, kaolin clay, talc, diatomaceous earth, or the like.
  • the content of the filler may be 20 parts by weight to 80 parts by weight, 30 parts by weight to 65 parts by weight, and 45 parts by weight to 55 parts by weight, based on 100 parts by weight of the acrylic copolymer. There is an effect of excellent physical properties.
  • the acrylic copolymer composition according to the present invention may further contain sulfur to enhance the blending crosslinking effect.
  • the acrylic copolymer composition may optionally further include a crosslinking agent and a crosslinking accelerator.
  • the crosslinking agent may be an amine compound, for example, a polyvalent amine compound.
  • polyvalent amine compound examples include an aliphatic polyvalent amine crosslinking agent and an aromatic polyvalent amine crosslinking agent.
  • Examples of the aliphatic polyvalent amine crosslinking agent include hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-disinnamylden-1,6-hexanediamine.
  • aromatic polyvalent amine crosslinking agent 4,4'-methylene dianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-(m- Phenylenediisopropylidene) Gianiin, 4,4'-(p-phenylenediisopropylidene) Gianiin, 2,2'-bis (4-(4-aminophenoxy) phenyl] propane, 4,4' -Diaminobenzanilide, 4,4'-bis(4-aminophenoxy) biphenyl, m-xylene diamine, p-xylene diamine, 1,3,5-benzene triamine, 1,3,5-benzene tri And aminomethyl.
  • the content of the crosslinking agent may be 0.05 parts by weight to 20 parts by weight, 0.1 parts by weight to 10 parts by weight, and 0.3 parts by weight to 6 parts by weight based on 100 parts by weight of the acrylic copolymer, and the formation of the crosslinked product is maintained within this range. It is easy to use, and has an excellent effect of elasticity.
  • the crosslinking accelerator may be a crosslinking accelerator that can be used in combination with the polyvalent amine crosslinking agent, and the base dissociation constant at 25° C. in water may be 10 to 106, or 12 to 106.
  • the crosslinking accelerator may include a guanidine compound, an imidazole compound, a quaternary onium salt, a tertiary phosphine compound, and an alkali metal salt of a weak acid.
  • the guanidine compound include 1,3-diphenyl guanidine, di-o-thryl guanidine, and the like.
  • the imidazole compound include 2-methylimidazole and 2-phenylimidazole.
  • the quaternary onium salt include tetra n-butyl ammonium bromide, octadecyl trin-butyl ammonium bromide, and the like.
  • Triethylene diamine, 1,8-diaza-bicyclo[5.4.0]undecene-7 etc. are mentioned as a polyhydric tertiary amine compound.
  • the tertiary phosphine compound include triphenyl phosphine, tri p-trylphosphine, and the like.
  • the alkali metal salt of the weak acid include inorganic weak acid salts such as sodium or potassium phosphate and carbonate, or organic weak acid salt such as stearic acid salt and lauryl acid salt.
  • the content of the crosslinking accelerator may be 0.1 parts by weight to 20 parts by weight, 0.2 parts by weight to 15 parts by weight, or 0.3 parts by weight to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer. It can be properly maintained, and the tensile strength of the crosslinked product is excellent.
  • the acrylic copolymer composition according to the present invention may further include additives such as a reinforcing material, an anti-aging agent, a light stabilizer, a plasticizer, a lubricant, an adhesive, a lubricant, a flame retardant, a flame retardant, an antistatic agent, and a colorant, if necessary.
  • additives such as a reinforcing material, an anti-aging agent, a light stabilizer, a plasticizer, a lubricant, an adhesive, a lubricant, a flame retardant, a flame retardant, an antistatic agent, and a colorant, if necessary.
  • the mixing of the acrylic copolymer composition according to the present invention may be carried out by a suitable mixing method such as roll mixing, Van Barry mixing, screw mixing, and solution mixing, and a specific example may be carried out by a roll mixing method.
  • the order of mixing is not particularly limited, but after sufficiently mixing components that are difficult to react or decompose by heat, as a component that is easy to react with heat or a component that is easily decomposed, for example, a crosslinking agent, etc., may be mixed in a short time at a temperature at which no reaction or decomposition occurs. .
  • the acrylic copolymer composition according to the present invention is kneaded with a roll, the degree of adhesion of the rubber to the roll is small and the workability is excellent.
  • the method of molding the acrylic copolymer composition according to the present invention may be performed by compression molding, injection molding, transfer molding, or extrusion molding.
  • the crosslinking method may be selected according to the shape of the crosslinked product, and may be performed by a method of simultaneously performing molding and crosslinking, a method of crosslinking after molding, and the like. Since the acrylic copolymer composition in the present invention uses an acrylic copolymer having the above configuration, the flowability of the acrylic copolymer is excellent during molding, the degree of burr generation is low during molding, and the molding precision of the obtained molded article is high. have.
  • the acrylic copolymer composition according to the present invention can be prepared as a crosslinked product by heating, and when the acrylic copolymer of the present invention is crosslinked, it is formed into a desired shape through a molding or extrusion process, or simultaneously or subsequently cured to produce an article. can do.
  • the manufactured article may be used as various automobile parts such as rubber for an engine mount, a transmission seal, and a crankshaft seal.
  • Example 1 the same method as in Example 1, except that 0.001 parts by weight of allyl methacrylate (AMA) was added instead of 0.001 parts by weight of divinyl benzene (Divinylbezene, DVB) when preparing the acrylic copolymer. It was carried out with.
  • AMA allyl methacrylate
  • DVB divinyl benzene
  • Example 1 when preparing the acrylic copolymer, it was carried out in the same manner as in Example 1, except that 0.005 parts by weight of divinylbenzene (Divinylbezene, DVB) was added instead of 0.001 parts by weight.
  • DVB divinylbenzene
  • Example 1 when preparing the acrylic copolymer, it was carried out in the same manner as in Example 1, except that 0.01 parts by weight of divinylbenzene (Divinylbezene, DVB) was added instead of 0.001 parts by weight.
  • DVB divinylbenzene
  • Example 2 it was carried out in the same manner as in Example 1, except that 0.05 parts by weight of allyl methacrylate (AMA) was added instead of 0.001 parts by weight.
  • AMA allyl methacrylate
  • Example 2 it was carried out in the same manner as in Example 1, except that 0.1 parts by weight of allyl methacrylate (AMA) was added instead of 0.001 parts by weight.
  • AMA allyl methacrylate
  • Example 1 when preparing the acrylic copolymer, it was carried out in the same manner as in Example 1, except that 0.06 parts by weight of divinylbenzene (Divinylbezene, DVB) was added instead of 0.001 parts by weight.
  • DVB divinylbenzene
  • Example 1 when preparing the acrylic copolymer, it was carried out in the same manner as in Example 1, except that 1.0 part by weight of divinylbenzene (Divinylbezene, DVB) was added instead of 0.001 part by weight.
  • 1.0 part by weight of divinylbenzene Divinylbezene, DVB
  • Example 1 the preparation of the acrylic copolymer was carried out in the same manner as in Example 1, except that divinyl benzene (DVB) was not added.
  • DVD divinyl benzene
  • Example 1 when preparing the acrylic copolymer, it was carried out in the same manner as in Example 1, except that 0.0001 parts by weight of divinylbenzene (Divinylbezene, DVB) was added instead of 0.001 parts by weight.
  • DVB divinylbenzene
  • Example 1 when preparing the acrylic copolymer, it was carried out in the same manner as in Example 1, except that 2.0 parts by weight of divinylbenzene (Divinylbezene, DVB) was added instead of 0.001 parts by weight.
  • DVB divinylbenzene
  • Pattern viscosity (ML1+4, 100 °C) MV-2000 (ALPHA Technologies) was measured using a Rotor Speed 2 ⁇ 0.02 rpm, Large Rotor at 100 °C, and the sample used at this time was room temperature (23 ⁇ 3 °C) for more than 30 minutes, collected 27 ⁇ 3 g, filled it inside the die cavity, and operated the platen to measure for 4 minutes.
  • Crosslinking density (Torque (dNm)): The difference between the initial torque value (ML) and the final torque value (MH) by crosslinking the copolymer through the roll milling process after mixing at 180°C for 30 minutes through a moving die rheometer (MDR). Crosslinking density was evaluated through.
  • test piece was put in 500 mL of the test liquid, and it was installed so that all the test pieces were immersed in the liquid. This was put in an oven and heated at 155°C for 168 hours. On the other hand, as the test liquid, 5W-30 oil was used.
  • the test specimen was taken out, the test liquid was wiped off, and the volume was measured to calculate the volume change rate ⁇ V (%) with the initial volume. The smaller the volume change rate, the better the oil resistance.
  • T0 is the spacing distance of the device
  • T1 is the sample thickness before the test
  • T2 is the sample thickness after the test.
  • Examples 1 to 8 including the polyfunctional monomer-derived portion according to the present invention in an appropriate range have excellent oil resistance and permanent compression reduction rate by improving crosslinking density.
  • Comparative Example 1 which did not include the polyfunctional monomer-derived portion according to the present invention, lowered the crosslinking density compared to the Examples, and accordingly, it was confirmed that the oil resistance and the permanent compression reduction rate characteristics were simultaneously lowered.
  • Comparative Example 2 whose content is less than the appropriate range, as in Comparative Example 1, has insignificant effect of improving oil resistance and permanent compression reduction characteristics, and thus can be confirmed in Examples. There was no expected improvement of the effect, and Comparative Example 3 whose content was higher than the appropriate range contained an excessively large amount of the polyfunctional monomer and lost the elasticity of the rubber, making it impossible to measure physical properties.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un copolymère acrylique et, plus spécifiquement, un copolymère acrylique comprenant : des motifs répétés dérivés d'un monomère principal ; et une fraction dérivée d'un monomère multifonctionnel, les motifs répétés dérivés d'un monomère principal comprenant un motif répété dérivé d'un monomère d'ester alkylique d'acide (méth)acrylique, une motif répété dérivé d'un monomère d'ester alcoxyalkylique d'acide (méth)acrylique, une motif répété dérivé d'un monomère réticulable, le monomère multifonctionnel contenant un groupe vinyle ou un groupe allyle, la fraction dérivée de monomère multifonctionnel étant contenue à hauteur de 0,0005 à 1 partie en poids pour 100 parties en poids du total des motifs répétés dérivés du monomère principal.
PCT/KR2020/011183 2019-10-11 2020-08-21 Copolymère acrylique, procédé pour le fabriquer et composition de copolymère acrylique le comprenant WO2021071085A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202080006757.5A CN113195566B (zh) 2019-10-11 2020-08-21 丙烯酸类共聚物、其制备方法和包含所述丙烯酸类共聚物的丙烯酸类共聚物组合物
US17/311,891 US20220025086A1 (en) 2019-10-11 2020-08-21 Acrylic Copolymer, Method for Manufacturing Same, and Acrylic Copolymer Composition Comprising Same
JP2021531646A JP7160474B2 (ja) 2019-10-11 2020-08-21 アクリル系共重合体、その製造方法、およびそれを含むアクリル系共重合体組成物

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KR20190125869 2019-10-11
KR10-2019-0125869 2019-10-11
KR1020200094657A KR102568623B1 (ko) 2019-10-11 2020-07-29 아크릴계 공중합체, 이의 제조방법 및 이를 포함하는 아크릴계 공중합체 조성물
KR10-2020-0094657 2020-07-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0615635B2 (ja) * 1985-08-30 1994-03-02 日本合成ゴム株式会社 新規なゴム組成物
JPH0739526B2 (ja) * 1985-01-31 1995-05-01 日本合成ゴム株式会社 加硫ゴム組成物
JP2005120143A (ja) * 2003-10-14 2005-05-12 Jsr Corp エポキシ基含有ゴム、該製造法、該組成物及び積層体
JP2015093926A (ja) * 2013-11-12 2015-05-18 日油株式会社 熱可塑性エラストマー及び熱可塑性樹脂組成物
KR20190085931A (ko) * 2016-11-30 2019-07-19 가부시키가이샤 오사카소다 아크릴 공중합체, 및 그의 가교물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0739526B2 (ja) * 1985-01-31 1995-05-01 日本合成ゴム株式会社 加硫ゴム組成物
JPH0615635B2 (ja) * 1985-08-30 1994-03-02 日本合成ゴム株式会社 新規なゴム組成物
JP2005120143A (ja) * 2003-10-14 2005-05-12 Jsr Corp エポキシ基含有ゴム、該製造法、該組成物及び積層体
JP2015093926A (ja) * 2013-11-12 2015-05-18 日油株式会社 熱可塑性エラストマー及び熱可塑性樹脂組成物
KR20190085931A (ko) * 2016-11-30 2019-07-19 가부시키가이샤 오사카소다 아크릴 공중합체, 및 그의 가교물

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