WO2021071085A1 - Acrylic copolymer, method for manufacturing same, and acrylic copolymer composition comprising same - Google Patents

Acrylic copolymer, method for manufacturing same, and acrylic copolymer composition comprising same Download PDF

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Publication number
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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Prior art keywords
monomer
weight
meth
acrylic copolymer
parts
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PCT/KR2020/011183
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French (fr)
Korean (ko)
Inventor
정용석
한정수
이지영
여승욱
신상진
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주식회사 엘지화학
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Priority claimed from KR1020200094657A external-priority patent/KR102568623B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080006757.5A priority Critical patent/CN113195566B/en
Priority to JP2021531646A priority patent/JP7160474B2/en
Priority to US17/311,891 priority patent/US20220025086A1/en
Publication of WO2021071085A1 publication Critical patent/WO2021071085A1/en

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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.

Abstract

The present invention relates to an acrylic copolymer and, more specifically, provides an acrylic copolymer comprising: main monomer-derived repeating units; and a multifunctional monomer-derived moiety, the main monomer-derived repeating units including a (meth)acrylic acid alkyl ester monomer-derived repeating unit, a (meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit, and a crosslinkable monomer-derived repeating unit, the multifunctional monomer containing a vinyl group or an allyl group, wherein the multifunctional monomer-derived moiety is contained in 0.0005-1 part by weight relative to 100 parts by weight of the total of the main monomer-derived repeating units.

Description

아크릴계 공중합체, 이의 제조방법 및 이를 포함하는 아크릴계 공중합체 조성물Acrylic copolymer, manufacturing method thereof, and acrylic copolymer composition comprising the same
관련출원과의 상호인용Mutual citation with related applications
본 출원은 2019년 10월 11일자 한국특허출원 제10-2019-0125869호 및 2020년 07월 29일자 한국특허출원 제10-2020-0094657호에 기초한 우선권의 이익을 주장하며, 해당 한국특허출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the interest of priority based on Korean Patent Application No. 10-2019-0125869 filed on October 11, 2019 and Korean Patent Application No. 10-2020-0094657 filed on July 29, 2020. All contents disclosed in the literature are included as part of this specification.
기술분야Technical field
본 발명은 아크릴계 공중합체에 관한 것으로, 보다 상세하게는 내유성 및 영구압축줄음율이 우수한 아크릴계 공중합체, 이의 제조방법 및 이를 포함하는 아크릴계 공중합체 조성물에 관한 것이다.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.
아크릴 고무는 아크릴산 에스테르를 주성분으로 하는 중합체로 내열성, 내유성 및 내오존성이 우수한 고무로 알려져 있으며 자동차 관련 분야 등에서 씰, 호스, 튜브, 벨트 등의 부품소재로 넓게 이용된다. 아크릴 고무는 소량이지만 자동차의 성능을 좌우하는 중요한 부분에 주로 사용되며, 그 특성상 진동 및 소음이 발생되는 부위에 적용되는 부분과 내열성 및 내유성이 필요한 부위에 적용되는 부분 등 중요한 부품으로 자리 잡고 있다.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.
아크릴 고무는 고무 부품으로서 사용할 수 있도록 가교시켜 탄성이 필요하며, 고온 하에서 내열성 및 내유성이 우수해야 한다. 최근, 내연기관의 고출력화나 배기가스 등에 의해 내연기관 주위 열적 환경조건이 가혹한 것 및 엔진 오일이 고온 조건하에서 진행하는 것 등에서 고무 부품의 성능 향상이 요구되고 있다. 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.
이와 같이 다양한 용도로 이용되고 있는 가교성 아크릴 고무는 우수한 내유성과 함께 일정수준의 고무 물성인 탄성을 필요로 한다. 또한 위 사용 용도에 적합한 내구성을 구현하기 위해서는 아크릴 고무의 높은 가교밀도가 요구되고 있다.Crosslinkable acrylic rubber used for various purposes as described above requires excellent oil resistance and elasticity, which is a certain level of rubber properties. In addition, high crosslinking density of acrylic rubber is required in order to realize durability suitable for the above use.
본 발명에서 해결하고자 하는 과제는, 상기 발명의 배경이 되는 기술에서 언급한 문제들을 해결하기 위하여, 내유성이 우수하고 영구압축줄음율이 적은 아크릴계 공중합체 조성물을 제공하는 것을 목적으로 한다.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.
상기의 과제를 해결하기 위한 본 발명의 일 실시예에 따르면, 본 발명은 주단량체 유래 반복단위 및 다관능성 단량체 유래부를 포함하고, 상기 주단량체 유래 반복단위는 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래 반복단위를 포함하며, 상기 다관능성 단량체는 비닐기 또는 알릴기를 포함하고, 상기 다관능성 단량체 유래부는 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.0005 내지 1 중량부로 포함되는 아크릴계 공중합체를 제공한다. According to an embodiment of the present invention for solving the above problems, 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.
또한, (메타)아크릴산 알킬 에스테르 단량체, (메타)아크릴산 알콕시 알킬 에스테르 단량체 및 가교성 단량체를 포함하는 주단량체 혼합물을 제조하는 단계; 및 상기 주단량체 혼합물에 다관능성 단량체를 투입하고 중합하는 단계를 포함하고, 다관능성 단량체는 상기 주단량체 혼합물 전체 100 중량부에 대하여 0.0005 내지 1 중량부로 투입되는 아크릴계 공중합체의 제조방법을 제공한다.In addition, 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.
본 발명에 따른 다관능성 단량체를 포함하는 아크릴계 공중합체는 중합물의 가교밀도를 향상시켜 내유성이 우수하고 고무의 특징인 탄성력은 유지하여 영구압축줄음율이 작은 효과가 있다.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.
본 발명의 설명 및 청구범위에서 사용된 용어나 단어는, 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the description and claims of the present invention should not be construed as being limited to a conventional or dictionary meaning, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.
본 발명에서 용어 '유래 반복단위' 및 '유래부'는 어떤 물질로부터 기인한 성분, 구조 또는 그 물질 자체를 나타내는 것일 수 있고, 구체적인 예로, '유래 반복단위'는 중합체의 중합 시, 투입되는 단량체가 중합 반응에 참여하여 중합체 내에서 이루는 반복단위를 의미하는 것일 수 있으며, '유래부'는 중합체의 중합 시, 투입되는 연쇄 이동제가 중합 반응에 참여하여 중합물의 연쇄이동 반응을 유도하는 것일 수 있다.In the present invention, 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. .
본 발명에서 용어 '고무'는 탄성을 가지는 가소성 물질을 나타내는 것으로, 러버, 엘라스토머, 또는 합성 라텍스 등을 의미하는 것일 수 있다.In the present invention, the term'rubber' refers to a plastic material having elasticity, and may mean rubber, elastomer, or synthetic latex.
본 발명에서 용어 '공중합체(copolymer)'는 공단량체가 공중합되어 형성된 공중합체를 모두 포함하는 의미일 수 있고, 구체적인 예로, 랜덤 공중합체 및 블록 공중합체를 모두 포함하는 의미하는 것일 수 있다.In the present invention, 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.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
본 발명에 따른 아크릴계 공중합체는 주단량체 유래 반복단위, 및 다관능성 단량체 유래부를 포함하는 것일 수 있다.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.
본 발명의 일 실시예에 따르면, 상기 주단량체 유래 반복단위는 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래 반복단위를 포함할 수 있다.According to an embodiment of the present invention, 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. .
본 발명의 일 실시예에 따르면, 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위는 아크릴계 공중합체 내에서 유리전이 온도를 조절하여 최종 제품에서의 작업성, 내열성 및 내한성을 증가시키는 역할을 하는 성분으로서, 탄소수 1 내지 8의 알킬기를 함유하는 (메타)아크릴산 알킬 에스테르 단량체일 수 있다. 이때, 상기 탄소수 1 내지 8의 알킬기는 탄소수 1 내지 8의 선형 또는 고리형 알킬기를 포함하는 의미일 수 있다. 구체적인 예로, 상기 (메타)아크릴산 알킬 에스테르 단량체는 (메타)아크릴산 메틸, (메타)아크릴산 에틸, (메타)아크릴산 프로필, (메타)아크릴산 이소프로필, (메타)아크릴산 n-부틸, (메타)아크릴산 이소부틸, (메타)아크릴산 n-아밀, (메타)아크릴산 아이소아밀, (메타)아크릴산 n-헥실, (메타)아크릴산 2-에틸헥실, (메타)아크릴산 사이클로헥실 등일 수 있다. 여기서, (메타)아크릴산 알킬 에스테르 단량체는 1종 또는 2종 이상을 조합하여 사용할 수 있으며, 구체적인 예로, (메타)아크릴산 에틸, (메타)아크릴산 n-부틸 단량체 등일 수 있다.According to an embodiment of the present invention, 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. In this case, the alkyl group having 1 to 8 carbon atoms may mean including a linear or cyclic alkyl group having 1 to 8 carbon atoms. In a specific example, 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. Here, 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.
상기 주단량체 유래 반복단위 내 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위의 함량은 60 중량% 내지 95 중량%, 75 중량% 내지 93 중량%, 또는 80 중량% 내지 90 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 작업성, 내열성 및 내한성이 우수한 효과가 있다.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.
상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위는 아크릴계 공중합체 내에서 유리전이 온도를 조절하여 최종 제품에서의 작업성, 내열성 및 내한성을 증가시키는 역할을 하는 성분으로서, 탄소수 1 내지 8의 알콕시알킬기를 함유하는 (메타)아크릴산 알킬 에스테르 단량체를 의미하는 것일 수 있다. 구체적인 예로, 상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체는 (메타)아크릴산 메톡시메틸, (메타)아크릴산 에톡시메틸, (메타)아크릴산 2-에톡시에틸, (메타)아크릴산 2-부톡시에틸, (메타)아크릴산2-메톡시에틸, (메타)아크릴산 2-프로폭시에틸, (메타)아크릴산 3-메톡시 프로필, (메타)아크릴산 4-메톡시부틸 등일 수 있다. 구체적인 예로, 상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체는 (메타)아크릴산 2-메톡시에틸일 수 있다.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. In a specific example, 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. As a specific example, the (meth)acrylic acid alkoxy alkyl ester monomer may be (meth)acrylic acid 2-methoxyethyl.
상기 주단량체 유래 반복단위 내 상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위의 함량은 1 중량% 내지 35 중량%, 7 중량% 내지 25 중량%, 또는 10 중량% 내지 20 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 작업성 및 내유성이 우수한 효과가 있다.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.
한편, 본 발명에 따른 상기 주단량체 유래 반복단위에 포함되는 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위 및 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위의 총 함량은 80 중량% 내지 99.9 중량%, 85 중량% 내지 99.9 중량% 또는 90 중량% 내지 99.5 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 작업성 내한성 및 내열성이 우수한 효과가 있다.Meanwhile, 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.
상기 가교성 단량체 유래 반복단위는 아크릴계 공중합체 내 가교성 관능기를 부여하기 위한 성분으로서, 부텐디온산 모노에스테르 단량체, 에폭시기 함유 단량체 및 할로겐 함유 단량체로 이루어진 군에서 선택되는 1종 이상일 수 있다.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.
상기 부텐디온산 모노에스테르 단량체는 부텐디온산, 즉 말레산 또는 푸마르산의 카르복실기와 알코올을 반응시켜 얻어진 말레산 모노에스테르 단량체 또는 푸마르산 모노에스테르 단량체일 수 있다. 상기 말레산 모노에스테르 단량체는 말레산 모노메틸, 말레산 모노에틸, 말레산 모노프로필, 말레인산 모노부틸, 말레산 모노펜틸, 말레산 모노데실 등의 말레산 모노알킬에스테르 단량체； 말레산 모노사이클로펜틸, 말레산 모노사이클로헥실, 말레산 모노사이클로헵틸, 말레산 모노사이클로옥틸, 말레산 모노메틸 사이클로헥실, 말레산 모노- 3,5-디메틸사이클로헥실, 말레산 모노디사이클로펜타닐, 말레산 모노이소보닐 등의 말레산 모노사이클로알킬 에스테르 단량체； 말레산 모노사이클로펜테닐, 말레산 모노사이클로헥세닐, 말레산 모노사이클로헵테닐, 말레산 모노사이클로옥테닐, 말레인산 디 사이클로펜타디에닐 등의 말레산 모노사이클로알케닐 에스테르 단량체; 등일 수 있다. 상기 푸마르산 모노에스테르 단량체는 푸마르산 모노메틸, 푸마르산 모노에틸, 푸마르산 모노프로필, 푸마르산 모노부틸, 푸마르산 모노헥실, 푸마르산 모노옥틸 등의 푸마르산 모노알킬에스테르 단량체； 푸마르산 모노사이클로펜틸, 푸마르산 모노사이클로헥실, 푸마르산 모노사이클로헵틸, 푸마르산 모노사이클로옥틸, 푸마르산 모노메틸 사이클로헥실, 푸마르산 모노- 3,5-디메틸사이클로헥실, 푸마르산 디사이클로펜타닐, 후말산이소보닐 등의 푸마르산 모노사이클로알킬 에스테르 단량체； 푸마르산 모노사이클로펜테닐, 푸마르산 모노사이클로헥세닐, 푸마르산 모노사이클로헵테닐, 푸마르산 모노사이클로옥테닐, 푸마르산 모노디사이클로펜타디에닐 등의 푸마르산 모노사이클로알케닐 에스테르 단량체 등일 수 있다. 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 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 monocyclohexenyl, fumaric acid monocycloheptenyl, fumaric acid monocyclooctenyl, and fumaric acid monodicyclopentadienyl.
상기 에폭시기 함유 단량체는 글리시딜(메타) 아크릴레이트, 비닐글리시딜에테르, 알릴글리시딜에테르, 메타크릴 글리시딜에테르 등일 수 있다. 구체적인 예로, 상기 에폭시기 함유 단량체는 글리시딜(메타) 아크릴레이트, 알릴글리시딜에테르 등일 수 있다. The epoxy group-containing monomer may be glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, and the like. As a specific example, the epoxy group-containing monomer may be glycidyl (meth) acrylate, allyl glycidyl ether, or the like.
상기 할로겐 함유 단량체는 비닐클로로아세테이트, 비닐 브로모 아세테이트, 알릴 클로로 아세테이트, 비닐 클로로 프로피오네이트, 비닐 클로로 부틸레이트, 비닐 브로모 부틸레이트, 2-클로로 아크릴산에틸, 3-클로로 프로필아크릴레이트, 4-클로로부틸 아크릴레이트, 2-클로로 에틸메타크릴레이트, 2-브로모 아크릴산에틸, 2-요오드 아크릴산에틸, 2-클로로에틸비닐에테르, 클로로 메틸 비닐 에테르, 4-클로로-2-부테닐 아크릴레이트, 비닐 벤질 클로라이드, 5-클로로메틸-2-노르보르넨, 5-클로로아세톡시 메틸-2-노르보르넨 등일 수 있다. 구체적인 예로, 상기 할로겐 함유 단량체는 비닐클로로아세테이트, 비닐 벤질 클로라이드, 2-클로로 아크릴산에틸, 2-클로로에틸비닐에테르 등일 수 있다.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. As a specific example, the halogen-containing monomer may be vinyl chloroacetate, vinyl benzyl chloride, 2-chloro ethyl acrylate, 2-chloroethyl vinyl ether, or the like.
상기 주단량체 유래 반복단위 내 가교성 단량체 유래 반복단위의 함량은 0.1 내지 20 중량%, 0.1 중량% 내지 15 중량% 또는 0.5 중량% 내지 10 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 가교밀도가 높고, 기계적 특성이 우수하며, 얻어진 가교물의 신장이 향상될 뿐만 아니라, 압축 영구 변형을 방지하는 효과가 있다.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.
상기 주단량체 유래 반복단위는 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래 반복단위 이외에 상기 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위 및 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위와 공중합 가능한 다른 단량체 유래 반복단위를 더 포함할 수 있다.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.
상기 다관능성 단량체 유래부는 아크릴계 공중합체 제조 시, 단량체 간의 가교를 유도하여 중합물의 가교밀도를 높이는 성분으로서, 두 개 이상의 바이닐기(vinyl group)와 알릴기(allyl group)를 함유하는 가교제로 유래된 것일 수 있다. 구체적인 예로 다관능성 단량체로는 디비닐벤젠, 1,4-디비닐옥시부탄, 디비닐술폰, 디알릴프탈레이트, 디알릴아크릴아미드, 트리알릴(이소)시아누레이트, 트리알릴트리멜리테이트 등의 알릴 화합물, 헥산디올디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 1,3-부탄디올메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 펜타에릴트리톨테트라(메타)아크릴레이트, 펜타에릴트리톨트리(메타)아크릴레이트, 펜타에릴트리톨디(메타)아크릴레이트, 트리메틸올프로판, 트리(메타)아크릴레이트, 디펜타에릴트리톨헥사(메타)아크릴레이트, 디펜타에릴트리톨펜타(메타)아크릴레이트, 글리세롤트리(메타)아크릴레이트, 알릴(메타)아크릴레이트 등을 들 수 있다. 본 발명에서는 상기 다관능성 단량체를 단독 혹은 2종 이상 혼합하여 사용할 수 있다. 구체적인 예로, 상기 다관능성 단량체는 디비닐벤젠 또는 알릴메타크릴레이트일 수 있다.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. Can be. Specific examples of polyfunctional monomers include allyl such as divinylbenzene, 1,4-divinyloxybutane, divinyl sulfone, diallylphthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate, etc. Compound, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol methacrylate, 1,6 -Hexanediol dimethacrylate, pentaerythritol tetra(meth)acrylate, pentaeryltritoltri(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane, tri(meth)acrylate ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaeryl tritol penta (meth) acrylate, glycerol tri (meth) acrylate, allyl (meth) acrylate, and the like. In the present invention, the polyfunctional monomer may be used alone or in combination of two or more. As a specific example, the polyfunctional monomer may be divinylbenzene or allyl methacrylate.
상기 다관능성 단량체 유래부의 함량은 상기 주단량체 유래 반복단위 100 중량부에 대하여, 0.0005 중량부 내지 1.0 중량부, 0.001 중량부 내지 0.8 중량부, 또는 0.001 중량부 내지 0.05 중량부일 수 있다. 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 가교밀도가 향상될 수 있으며, 그에 따라, 내유성이 높아지고 영구압축줄음율은 낮아지면서, 아크릴계 공중합체가 과도하게 딱딱해지는 것을 방지하여 작업성 및 가공성 또한 우수한 효과가 있다.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. Within this range, 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.
상기 아크릴계 공중합체의 중량평균 분자량은 200,000 g/mol 내지 4,000,000 g/mol, 300,000 g/mol 내지 3,000,000 g/mol 또는 500,000 g/mol 내지 2,500,000 g/mol일 수 있고, 이 범위 내에서 아크릴계 공중합체의 제조 시간 절감 및 우수한 기계적 물성 구현이 가능한 효과가 있다.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.
상기 아크릴계 공중합체의 무늬 점도(ML1+4, 100 ℃)는 10 내지 70, 20 내지 60 또는 25 내지 50일 수 있으며, 이 범위 내에서 작업성이 우수한 효과가 있다.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.
본 발명에 따르면, 아크릴계 공중합체 제조방법이 제공된다. 본 발명에 따른 아크릴계 공중합체 제조방법은, (메타)아크릴산알킬에스테르 단량체, (메타)아크릴산알콕시알킬에스테르 단량체 및 가교성 단량체를 포함하는 주단량체 혼합물을 제조하는 단계; 및 상기 주단량체 혼합물 전체 100 중량부에 대하여, 다관능성 단량체 0.0005 중량부 내지 1 중량부를 투입하고 중합하는 단계를 포함할 수 있다. 여기서, 상기 다관능성 단량체는 두 개 이상의 바이닐기(vinyl group)와 알릴기(allyl group)를 함유하는 가교제를 함유하는 것일 수 있다. According to the present invention, a method for producing an acrylic copolymer is provided. The method for preparing an acrylic copolymer according to the present invention 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. Here, the polyfunctional monomer may contain a crosslinking agent containing two or more vinyl groups and allyl groups.
상기 다관능성 단량체의 함량은 상기 주단량체 혼합물 전체 100 중량부에 대하여, 0.0005 중량부 내지 1.0 중량부, 0.001 중량부 내지 0.8 중량부, 또는 0.001 중량부 내지 0.05 중량부일 수 있다. 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 가교밀도가 향상될 수 있으며, 그에 따라, 내유성이 높아지고 영구압축줄음율은 낮아지면서, 아크릴계 공중합체가 과도하게 딱딱해지는 것을 방지하여 작업성 및 가공성 또한 우수한 효과가 있다.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. Within this range, 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.
상기 주단량체 혼합물을 제조하는 단계는, 아크릴계 공중합체의 주쇄를 이루는 단량체를 배합하는 단계일 수 있으며, 상기 주단량체 혼합물을 형성하는 단량체의 종류 및 함량은 앞서 기재한 주단량체 유래 반복단위를 형성하기 위한 단량체의 종류 및 함량과 동일한 것일 수 있다.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.
상기 아크릴계 공중합체는 유화 중합, 괴상 중합, 현탁 중합, 용액 중합 등의 방법을 이용하여 실시될 수 있고, 개시제, 유화제, 중합 정지제, 이온 교환수, 분자량 조절제, 활성화제, 산화환원촉매 등의 첨가제를 추가로 이용하여, 회분식, 반회분식, 연속식 등의 유화 중합 방법에 의해 실시될 수 있다.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.
상기 개시제는 일례로 과황산나트륨, 과황산칼륨, 과황산암모늄, 과인산칼륨, 과산화 수소 등의 무기 과산화물; 디이소프로필벤젠 하이드로퍼옥사이드, t-부틸 하이드로퍼옥사이드, 큐멘 하이드로퍼옥사이드, p-멘탄 하이드로퍼옥사이드, 디-t-부틸 퍼옥사이드, t-부틸쿠밀 퍼옥사이드, 아세틸 퍼옥사이드, 이소부틸 퍼옥사이드, 옥타노일퍼옥사이드, 벤조일 퍼옥사이드, 3,5,5-트리메틸헥산올 퍼옥사이드, t-부틸 퍼옥시 이소부틸레이트 등의 유기 과산화물; 아조비스 이소부티로니트릴, 아조비스-2,4-디메틸발레로니트릴, 아조비스시클로헥산카르보니트릴, 아조비스 이소낙산(부틸산)메틸 등의 질소 화합물 등일 수 있다. 이들 중합 개시제는 단독 또는 2종 이상을 조합해 사용할 수 있다. 이러한 개시제는 주단량체 혼합물 100 중량부에 대하여, 0.005 중량부 내지 0.2 중량부로 사용될 수 있다.Examples of the initiator 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) methyl. These polymerization initiators can be used alone or in combination of two or more. These initiators may be used in an amount of 0.005 parts by weight to 0.2 parts by weight based on 100 parts by weight of the main monomer mixture.
한편, 유기 과산화물 또는 무기 과산화물 개시제는 환원제와의 조합으로 레독스계 중합 개시제로서 사용할 수 있다. 이 환원제로서는 특별히 제한되지 않지만 황산제일철, 나프텐산 제1 구리 등의 환원 상태에 있는 금속 이온을 함유하는 화합물；메탄설폰산 나트륨 등의 설폰산 화합물；디메틸아닐린 등의 아민 화합물；등을 들 수 있다. 이들의 환원제는 단독으로 또는 2종 이상을 조합해 이용할 수 있다. 상기 환원제는 과산화물 1 중량부에 대하여, 0.005 중량부 내지 20 중량부로 사용될 수 있다.Meanwhile, an organic peroxide or inorganic peroxide initiator can be used as a redox polymerization initiator in combination with a reducing agent. Although it does not specifically limit as this 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.
상기 유화제는 음이온계 유화제, 양이온계 유화제 및 비이온계 유화제로 이루어지는 군으로부터 1종 이상 선택될 수 있으며, 구체적인 예로, 폴리옥시에틸렌 알킬에테르, 폴리옥시에틸렌 알킬페놀 에테르, 폴리옥시에틸렌 알킬 에스테르, 폴리옥시에틸렌소르비탄 알킬에스테르 등의 비이온성 유화제；미리스틴산, 팔미트산, 올레산, 리놀렌산 등의 지방산의 염, 도데실 벤젠설폰산 나트륨 등의 알킬 벤젠설폰산염, 고급 알코올 황산에스테르염, 알킬술포숙신산염 등의 음이온성 유화제；알킬 트리메틸 암모늄 클로라이드, 디알킬암모늄 클로라이드, 벤질 암모늄 클로라이드 등의 양이온성 유화제；α,β-불포화 카르복실산의 설포 에스테르, α,β-불포화 카르복실산의 설페이트 에스테르, 설포 알킬 아릴 에테르 등의 공중합성 유화제 등을 들 수 있다. 그 중에서도, 음이온성 유화제가 적합하게 이용된다. 상기 유화제는 주단량체 혼합물 100 중량부에 대하여, 0.1 중량부 내지 10 중량부로 사용될 수 있다. 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 α,β-unsaturated carboxylic acids, sulfate esters of α,β-unsaturated carboxylic acids And copolymerizable emulsifiers such as sulfoalkyl aryl ethers. Among them, anionic emulsifiers are suitably used. The emulsifier may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the main monomer mixture.
상기 이온교환수로는 물을 사용할 수 있으며, 상기 이온교환수는 주단량체 혼합물 100 중량부에 대하여, 100 중량부 내지 400 중량부로 사용될 수 있다.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.
상기 분자량 조절제는 일례로 a-메틸스티렌다이머, t-도데실머캅탄, n-도데실머캅탄, 옥틸머캅탄 등의 머캅탄류; 사염화탄소, 염화메틸렌, 브롬화 메틸렌 등의 할로겐화 탄화수소; 테트라에틸 디우람 디설파이드, 디펜타메틸렌 디우람 디설파이드, 디이소프로필키산토겐 디설파이드 등의 유황 함유 화합물 등일 수 있다. 상기 분자량 조절제는 주단량체 혼합물 100 중량부에 대하여, 0.1 중량부 내지 3 중량부로 사용될 수 있다.Examples of the molecular weight modifier 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.
상기 활성화제는 일례로 하이드로아황산나트륨, 소듐 포름알데히드 설폭시레이트, 소디움에틸 렌디아민 테트라아세테이트, 황산 제1 철, 락토오즈, 덱스트로오스, 리놀렌산나트륨, 및 황산나트륨 중에서 선택된 1 종 이상일 수 있다. 상기 활성화제는 주단량체 혼합물 100 중량부에 대하여, 0.01 중량부 내지 0.15 중량부로 사용될 수 있다.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.
상기 산화환원촉매는 일례로 소듐 포름알데하이드 설폭시레이트, 황산 제1철, 디소디움 에틸렌디아민테 트라아세테이트, 제2 황산구리 등일 수 있다. 상기 산화환원촉매는 주단량체 혼합물 100 중량부에 대하여, 0.01 중량부 내지 0.1 중량부로 사용될 수 있다.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.
본 발명에 따른 아크릴계 공중합체 조성물은 상기와 같이 수득된 아크릴계 공중합체 및 충전제를 포함할 수 있다.The acrylic copolymer composition according to the present invention may include the acrylic copolymer and filler obtained as described above.
상기 충전제는 카본블랙, 실리카, 카올린 클레이, 탤크, 규조토 등일 수 있다.The filler may be carbon black, silica, kaolin clay, talc, diatomaceous earth, or the like.
상기 충전제의 사용 함량은 아크릴계 공중합체 100 중량부에 대하여, 20 중량부 내지 80 중량부, 30 중량부 내지 65 중량부, 또한 45 중량부 내지 55 중량부일 수 있으며, 이 범위 내에서 작업성 및 기계적 물성이 우수한 효과가 있다.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.
한편, 본 발명에 따른 아크릴계 공중합체 조성물은 배합 가교 효과를 증진시키기 위해 황을 더 포함할 수 있다.On the other hand, the acrylic copolymer composition according to the present invention may further contain sulfur to enhance the blending crosslinking effect.
또한 상기 아크릴계 공중합체 조성물은 가교제 및 가교 촉진제를 선택적으로 더 포함할 수 있다. 상기 가교제는 아민 화합물, 구체적인 예로 다가 아민 화합물을 사용할 수 있다. In addition, 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.
다가 아민 화합물로서 구체적으로는 지방족 다가 아민 가교제, 방향족 다가 아민 가교제 등을 들 수 있다. Specific examples of the polyvalent amine compound include an aliphatic polyvalent amine crosslinking agent and an aromatic polyvalent amine crosslinking agent.
지방족 다가 아민 가교제로서는 헥사메틸렌디아민, 헥사메틸렌디아민 카바메이트, N,N'-디신나밀리덴-1,6-헥산디아민 등을 들 수 있다.Examples of the aliphatic polyvalent amine crosslinking agent include hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-disinnamylden-1,6-hexanediamine.
방향족 다가 아민 가교제로서는 4,4'-메틸렌 디아닐린, m-페닐렌디아민, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-(m-페닐렌디이소프로필리덴) 지아니 인, 4,4'-(p-페닐렌디이소프로필리덴) 지아니 인, 2,2'-비스〔4-(4-아미노페녹시) 페닐〕프로판, 4,4'-디아미노벤즈아닐리드, 4,4'-비스(4-아미노페녹시) 비페닐, m-크실렌 디아민, p-크실렌 디아민, 1,3,5-벤젠 트리아민, 1,3,5-벤젠 트리아미노메틸 등을 들 수 있다.As an 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.
상기 가교제의 사용 함량은 아크릴계 공중합체 100 중량부에 대하여, 0.05 중량부 내지 20 중량부, 0.1 중량부 내지 10 중량부, 또한 0.3 중량부 내지 6 중량부일 수 있으며, 이 범위 내에서 가교물의 형성 유지가 용이하며, 탄성이 우수한 효과가 있다.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.
상기 가교 촉진제는 상기 다가 아민 가교제와 조합해 이용할 수 있는 가교 촉진제일 수 있으며, 수중, 25 ℃에서의 염기 해리 상수가 10 내지 106, 또는 12 내지 106일 수 있다. 구체적인 예로, 상기 가교 촉진제는 구아니딘 화합물, 이미다졸 화합물, 제4급 오늄염, 제3급 포스핀 화합물, 약산의 알칼리 금속염 등을 들 수 있다. 구아니딘 화합물로서는 1,3-디페닐 구아니딘, 디-o-트릴 구아니딘 등을 들 수 있다. 이미다졸 화합물로서는2-메틸이미다졸,2-페닐이미다졸 등을 들 수 있다. 제4급 오늄염으로서는 테트라 n-부틸 암모늄 브로마이드, 옥타데실 트리n-부틸 암모늄 브로마이드 등을 들 수 있다.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. As a specific example, 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. Examples of the guanidine compound include 1,3-diphenyl guanidine, di-o-thryl guanidine, and the like. Examples of the imidazole compound include 2-methylimidazole and 2-phenylimidazole. Examples of the quaternary onium salt include tetra n-butyl ammonium bromide, octadecyl trin-butyl ammonium bromide, and the like.
다가 제3급 아민 화합물로서는 트리에틸렌 디아민, 1,8-디아자-비사이클로［5.4.0］운데센-7 등을 들 수 있다. 제3급 포스핀 화합물로서는 트리페닐 포스핀, 트리 p-트릴포스핀 등을 들 수 있다. 약산의 알칼리 금속염으로서는 나트륨 또는 칼륨의 인산염, 탄산염 등의 무기 약산염 혹은 스테아린산염, 라우릴산염등의 유기 약산염을 들 수 있다.Triethylene diamine, 1,8-diaza-bicyclo[5.4.0]undecene-7 etc. are mentioned as a polyhydric tertiary amine compound. Examples of the tertiary phosphine compound include triphenyl phosphine, tri p-trylphosphine, and the like. Examples of 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.
상기 가교 촉진제의 사용 함량은 아크릴계 공중합체 100 중량부에 대하여, 0.1 중량부 내지 20 중량부, 0.2 중량부 내지 15 중량부, 또는 0.3 중량부 내지 10 중량부일 수 있으며, 이 범위 내에서 가교 속도를 적절히 유지할 수 있고, 가교물의 인장강도가 우수한 효과가 있다.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.
본 발명에 따른 아크릴계 공중합체 조성물은 필요에 따라 보강재, 노화 방지제, 광안정제, 가소제, 윤활제, 점착제, 윤활제, 난연제, 방미제, 대전 방지제, 착색제 등의 첨가제가 더 포함될 수 있다.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.
본 발명에 따른 아크릴계 공중합체 조성물의 배합은 롤 혼합, 밴 배리 혼합, 스크류 혼합, 용액 혼합 등의 적당의 혼합 방법이 채택할 수 있고, 구체적인 예로 롤 혼합 방법으로 실시될 수 있다. 배합 순서는 특별히 제한되지 않지만 열로 반응이나 분해하기 어려운 성분을 충분히 혼합한 후, 열로 반응하기 쉬운 성분 혹은 분해하기 쉬운 성분으로서 예를 들어 가교제 등을 반응이나 분해가 일어나지 않는 온도에서 단시간에 혼합하면 좋다. 본 발명에 따른 아크릴계 공중합체 조성물은 롤로 혼련할 때 롤로의 고무의 부착 정도가 적고 작업성이 우수한 효과가 있다.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. . When 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.
또한, 본 발명에 따른 아크릴계 공중합체 조성물의 성형 방법은 압축 성형, 사출 성형, 트랜스퍼 성형 혹은 압출성형 등으로 실시될 수 있다. 또한 가교 방법은 가교물의 형상 등에 따라 선택하면 좋고 성형과 가교를 동시에 수행하는 방법, 성형 후에 가교를 하는 방법 등으로 실시될 수 있다. 본 발명에 아크릴계 공중합체 조성물은 상기 구성을 가지는 아크릴계 공중합체를 이용하기 때문에, 성형 시 아크릴계 공중합체의 유동성이 우수하고, 성형 시 버 발생 정도도 낮을 뿐만 아니라, 얻어진 성형체의 성형 정밀도가 높은 효과가 있다.In addition, 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. In addition, 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.
본 발명에 따른 아크릴계 공중합체 조성물은 가열함으로써 가교물로 제조할수 있으며, 본 발명의 아크릴계 공중합체는 가교되면, 성형 또는 압출 공정을 통해 원하는 형상으로 형성하거나 이와 동시에 또는 후속적으로 경화시킴으로써 물품을 제조할 수 있다. 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.
또한, 상기 제조된 물품은, 엔진 마운트용 고무, 트랜스미션 씰(seal), 크랭크 샤프트 씰 등 다양한 자동차 부품으로 사용될 수 있다.In addition, the manufactured article may be used as various automobile parts such as rubber for an engine mount, a transmission seal, and a crankshaft seal.
이하, 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 그러나, 하기 실시예는 본 발명을 예시하기 위한 것으로 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 통상의 기술자에게 있어서 명백한 것이며, 이들 만으로 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and that various changes and modifications can be made within the scope of the present invention and the scope of the technical idea are obvious to those skilled in the art, and the scope of the present invention is not limited thereto.
실시예Example
실시예 1 Example 1
<아크릴계 공중합체 제조><Preparation of acrylic copolymer>
중합 반응기에 부틸 아크릴레이트 32.0 중량%, 에틸 아크릴레이트 50.0 중량% 및 2-메톡시 에틸아크릴레이트 15.0 중량%, 비닐 클로로 아세테이트 3.0 중량%로 구성되는 주단량체 혼합물과 상기 주단량체 혼합물 100 중량부에 대하여 소듐 라우릴 설페이트 3.0 중량부, 소듐 메타비 설파이트 0.5 중량부, 큐멘 하이드로퍼옥사이드 0.01 중량부, 소듐 포름알데하이드 설폭시레이트 0.01 중량부, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부, 물 400 중량부를 넣은 후 40 ℃의 온도에서 중합을 개시하였다.In the polymerization reactor, based on 100 parts by weight of the main monomer mixture and the main monomer mixture consisting of 32.0% by weight of butyl acrylate, 50.0% by weight of ethyl acrylate, 15.0% by weight of 2-methoxy ethylacrylate, and 3.0% by weight of vinyl chloro acetate Sodium lauryl sulfate 3.0 parts by weight, sodium metabisulfite 0.5 parts by weight, cumene hydroperoxide 0.01 parts by weight, sodium formaldehyde sulfoxylate 0.01 parts by weight, divinylbezene (DVB) 0.001 parts by weight, water 400 parts by weight After adding the part, polymerization was initiated at a temperature of 40°C.
중합 전환율이 93%에 이르렀을 때 중합 정지제 0.3 중량부를 첨가하여 중합을 정지시켰다. 그 후 산화방지제를 첨가하고 65 ℃의 온도의 응집제를 첨가한 수상에서 응집하여 중합 아크릴 공중합체를 수득하였다.When the polymerization conversion rate reached 93%, 0.3 parts by weight of a polymerization terminator was added to stop the polymerization. Thereafter, an antioxidant was added and agglomerated in an aqueous phase to which a coagulant at a temperature of 65°C was added to obtain a polymerized acrylic copolymer.
<아크릴계 공중합체 조성물 제조><Preparation of acrylic copolymer composition>
상기 아크릴 공중합체 100 중량부를 Haake mixer를 통해 30rpm으로 50 ℃에서 30초 간 교반한 후 카본블랙 50 중량부, 스테아릭에시드 1.0 중량부, 산화방지제 2.0 중량부, 황 0.3 중량부, 포타슘 비누(potassium soap) 0.3 중량부, 소듐 비누(sodium soap) 2.5 중량부를 투입하고 90 ℃에서 360초 배합한 후 롤밀 장비를 통해 배합된 아크릴계 공중합체 조성물을 얻었다.After stirring 100 parts by weight of the acrylic copolymer at 50° C. for 30 seconds at 30 rpm through a Haake mixer, 50 parts by weight of carbon black, 1.0 parts by weight of stearic acid, 2.0 parts by weight of antioxidant, 0.3 parts by weight of sulfur, potassium soap (potassium soap) 0.3 parts by weight and 2.5 parts by weight of sodium soap were added and mixed at 90° C. for 360 seconds, and then the mixed acrylic copolymer composition was obtained through a roll mill equipment.
실시예 2Example 2
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 알릴메타크릴레이트(Allyl methacrylate, AMA) 0.001 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실시예 3Example 3
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 0.005 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실시예 4Example 4
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 0.01 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실시예 5Example 5
상기 실시예 2에서, 알릴메타크릴레이트(Allyl methacrylate, AMA) 0.001 중량부 대신 0.05 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실시예 6 Example 6
상기 실시예 2에서, 알릴메타크릴레이트(Allyl methacrylate, AMA) 0.001 중량부 대신 0.1 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실시예 7Example 7
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 0.06 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실시예 8Example 8
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 1.0 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
비교예 1Comparative Example 1
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB)을 투입하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
비교예 2Comparative Example 2
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 0.0001 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
비교예 3Comparative Example 3
상기 실시예 1에서, 아크릴계 공중합체 제조시, 디비닐벤젠(Divinylbezene, DVB) 0.001 중량부 대신 2.0 중량부를 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In 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.
실험예Experimental example
실험예 1Experimental Example 1
상기 실시예 및 비교예에서 제조된 아크릴계 공중합체 조성물의 무늬점도, 가교밀도, 내유성 및 영구압축줄음율을 하기와 같은 방법으로 측정하였고, 그 결과를 하기 표 1 및 2에 기재하였다.The pattern viscosity, crosslinking density, oil resistance, and permanent compression reduction rate of the acrylic copolymer compositions prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Tables 1 and 2 below.
* 무늬 점도(ML1+4, 100 ℃): MV-2000(ALPHA Technologies 社)를 이용하여 100 ℃에서 Rotor Speed 2±0.02 rpm, Large Rotor를 사용하여 측정하였으며, 이때 사용된 시료는 실온(23±3 ℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 다이 캐비티 내부에 채워 놓고 Platen을 작동시켜 4분 동안 측정하였다.* Pattern viscosity (ML1+4, 100 ℃): MV-2000 (ALPHA Technologies) was measured using a Rotor Speed 2±0.02 rpm, Large Rotor at 100 ℃, and the sample used at this time was room temperature (23± 3 ℃) for more than 30 minutes, collected 27±3 g, filled it inside the die cavity, and operated the platen to measure for 4 minutes.
* 가교 밀도(Torque (dNm)): 배합 후 롤밀 공정을 거친 공중합체를 Moving die rheometer(MDR)을 통해 180 ℃에서 30분 동안 가교하여 초기 토크 값(ML)과 최종 토크 값(MH)의 차를 통해 가교밀도를 평가하였다. * 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.
* 내유성 시험: 이 시험편에 대해서는 시트상의 아크릴 고무 가교물을 얻고, 얻어진 시트상의 아크릴 고무 가교물로부터 ASTM-412D에 준하여 덤벨형상의 시편을 제작하였다. * Oil resistance test: For this test piece, a sheet-shaped crosslinked acrylic rubber product was obtained, and a dumbbell-shaped specimen was prepared from the obtained sheet-shaped crosslinked acrylic rubber product according to ASTM-412D.
이 시험편을 시험용 액체 500mL에 넣어, 시험편이 모두 액 중에 침지되도록 설치하였다. 이를 오븐에 넣고, 155 ℃에서, 168시간, 가열을 행하였다. 한편, 시험용 액체로는, 5W-30 오일을 사용하였다.This 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.
가열 후, 시험용 시험편을 꺼내, 시험용 액체를 닦아낸 후, 체적을 측정하여, 초기 체적과의 체적 변화율 △V(%)를 계산하였다. 체적 변화율이 작은 편이, 내유성이 우수하다.After heating, the test specimen was taken out, the test liquid was wiped off, and the volume was measured to calculate the volume change rate ΔV (%) with the initial volume. The smaller the volume change rate, the better the oil resistance.
* 영구압축줄음률(%): 영구압축줄음률(C-세트)은 ASTM D395 방법 B에 따라 155 ℃에서 22시간 동안 25% 압축 조건 하에서 측정되었다. 영구압축줄음률은 하기 방정식을 사용하여 계산되었다:* Permanent compression reduction rate (%): The permanent compression reduction rate (C-set) was measured under 25% compression conditions at 155° C. for 22 hours according to ASTM D395 Method B. The permanent compression reduction rate was calculated using the following equation:
영구압축줄음률 = (T1-T2)/(T1-T0)*100% Permanent compression reduction rate = (T1-T2)/(T1-T0)*100%
여기서 T0는 장치의 간격 거리이고, T1은 시험 전 샘플 두께이고, T2는 시험 후 샘플 두께이다.Where T0 is the spacing distance of the device, T1 is the sample thickness before the test, and T2 is the sample thickness after the test.
구분division 실시예Example
1One 22 33 44 55 66 77 88
다관능성 단량체(중량부)Polyfunctional monomer (parts by weight) DVBDVB 0.0010.001 -- 0.0050.005 0.010.01 -- -- 0.060.06 1.01.0
AMAAMA -- 0.0010.001 -- -- 0.050.05 0.10.1 -- --
무늬점도(ML1+4, 100 ℃)Pattern viscosity (ML1+4, 100 ℃) 42.542.5 42.142.1 41.841.8 42.542.5 42.142.1 42.742.7 42.842.8 42.642.6
가교밀도(dNm)Crosslinking density (dNm) MLML 2.892.89 3.043.04 3.123.12 3.183.18 3.213.21 3.413.41 3.313.31 4.104.10
MHMH 16.3416.34 16.4716.47 16.5316.53 16.2916.29 16.3516.35 16.2516.25 16.1616.16 16.6916.69
MH-MLMH-ML 13.4513.45 13.4313.43 13.4113.41 13.1113.11 13.1413.14 12.8412.84 12.8512.85 12.5912.59
내유성 시험(ΔV(%))Oil resistance test (ΔV(%)) 3.053.05 2.972.97 2.732.73 2.512.51 2.392.39 2.852.85 3.153.15 3.513.51
영구압축줄음률(%)Permanent compression reduction rate (%) 23.523.5 23.823.8 23.223.2 22.822.8 22.222.2 24.124.1 24.524.5 24.824.8
구분division 비교예 Comparative example
1One 22 33
다관능성 단량체(중량부)Polyfunctional monomer (parts by weight) DVBDVB -- 0.000010.00001 2.02.0
AMAAMA -- -- --
무늬점도(ML1+4, 100 ℃)Pattern viscosity (ML1+4, 100 ℃) 42.342.3 42.742.7 측정 불가Not measurable
가교밀도(dNm)Crosslinking density (dNm) MLML 2.882.88 2.752.75 측정 불가Not measurable
MHMH 15.1115.11 15.0515.05 측정 불가Not measurable
MH-MLMH-ML 12.2312.23 12.3012.30 측정 불가Not measurable
내유성 시험(ΔV(%))Oil resistance test (ΔV(%)) 4.114.11 4.094.09 측정 불가Not measurable
영구압축줄음률(%)Permanent compression reduction rate (%) 26.526.5 26.826.8 측정 불가Not measurable
상기 표 1을 참조하면, 적정 범위의 본 발명에 따른 다관능성 단량체 유래부를 포함한 실시예 1 내지 8은 가교밀도가 향상됨으로써 내유성 및 영구압축줄음률이 우수한 것을 확인할 수 있다. Referring to Table 1, it can be seen that 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.
반면, 본 발명에 따른 다관능성 단량체 유래부를 포함하지 않은 비교예 1은 실시예들에 비하여 가교밀도가 저하되고, 이에 따라 내유성 및 영구압축줄음율 특성이 동시에 저하된 것을 확인할 수 있다. On the other hand, 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.
또한, 본 발명에 따른 다관능성 단량체 유래부를 포함하더라도, 그 사용 함량이 적정 범위보다 적은 비교예 2는 비교예 1과 마찬가지로 내유성 및 영구압축줄음율 특성 개선의 효과가 미미하여서 실시예들에서 확인할 수 있는 효과 개선을 기대할 수 없었으며, 그 사용 함량이 적정 범위보다 많은 비교예 3은 오히려 다관능성 단량체의 함량이 과도하게 많이 포함되어 고무의 탄성을 잃어버림으로써 물성의 측정이 불가하였다.In addition, even if the polyfunctional monomer-derived part according to the present invention is included, 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.
따라서, 본 발명에 따르면, 단량체 간의 가교밀도 향상에 따른 내유성 및 영구압축줄음률이 우수한 아크릴계 공중합체를 제공할 수 있음을 확인하였다.Therefore, according to the present invention, it was confirmed that it was possible to provide an acrylic copolymer having excellent oil resistance and permanent compression reduction rate by improving the crosslinking density between monomers.

Claims (10)

  1. 주단량체 유래 반복단위 및 다관능성 단량체 유래부를 포함하고,Including a repeating unit derived from the main monomer and a portion derived from a polyfunctional monomer,
    상기 주단량체 유래 반복단위는 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래 반복단위를 포함하며,The repeating unit derived from the main monomer includes 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,
    상기 다관능성 단량체는 비닐기 또는 알릴기를 포함하고,The polyfunctional monomer includes a vinyl group or an allyl group,
    상기 다관능성 단량체 유래부는 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.0005 내지 1 중량부로 포함되는 아크릴계 공중합체.The polyfunctional monomer-derived part is an acrylic copolymer containing 0.0005 to 1 part by weight based on the total 100 parts by weight of the repeating unit derived from the main monomer.
  2. 제1항에 있어서,The method of claim 1,
    상기 다관능성 단량체는 디비닐벤젠, 1,4-디비닐옥시부탄, 디비닐술폰, 디알릴프탈레이트, 디알릴아크릴아미드, 트리알릴(이소)시아누레이트, 트리알릴트리멜리테이트, 헥산디올디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 1,3-부탄디올메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 펜타에릴트리톨테트라(메타)아크릴레이트, 펜타에릴트리톨트리(메타)아크릴레이트, 펜타에릴트리톨디(메타)아크릴레이트, 트리메틸올프로판, 트리(메타)아크릴레이트, 디펜타에릴트리톨헥사(메타)아크릴레이트, 디펜타에릴트리톨펜타(메타)아크릴레이트, 글리세롤트리(메타)아크릴레이트, 알릴(메타)아크릴레이트로 이루어진 군에서 선택되는 1종 이상인 아크릴계 공중합체. The polyfunctional monomers are divinylbenzene, 1,4-divinyloxybutane, divinyl sulfone, diallylphthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate, hexanediol diacrylic. Ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol methacrylate, 1,6-hexanediol dimethacrylate Rate, pentaeryltritoltetra(meth)acrylate, pentaeryltritoltri(meth)acrylate, pentaeryltritoldi(meth)acrylate, trimethylolpropane, tri(meth)acrylate, dipenta At least one acrylic copolymer selected from the group consisting of erythritol hexa (meth) acrylate, dipenta erythritol penta (meth) acrylate, glycerol tri (meth) acrylate, and allyl (meth) acrylate .
  3. 제1항에 있어서,The method of claim 1,
    상기 다관능성 단량체는 디비닐벤젠 또는 알릴메타크릴레이트인 아크릴계 공중합체.The polyfunctional monomer is an acrylic copolymer of divinylbenzene or allyl methacrylate.
  4. 제1항에 있어서,The method of claim 1,
    상기 다관능성 단량체 유래부는 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.001 내지 0.05 중량부로 포함되는 아크릴계 공중합체. The polyfunctional monomer-derived part is an acrylic copolymer contained in an amount of 0.001 to 0.05 parts by weight based on 100 parts by weight of the total repeating unit derived from the main monomer.
  5. 제1항에 있어서,The method of claim 1,
    상기 가교성 단량체는 비닐클로로아세테이트, 비닐벤질클로라이드, 2-클로로 아크릴산에틸 및 2-클로로에틸비닐에테르로 이루어진 군에서 선택되는 1종 이상인 아크릴계 공중합체.The crosslinkable monomer is at least one acrylic copolymer selected from the group consisting of vinyl chloroacetate, vinylbenzyl chloride, 2-chloro ethyl acrylate, and 2-chloroethyl vinyl ether.
  6. 제5항에 있어서,The method of claim 5,
    상기 가교성 단량체 유래 반복단위는 주단량체 유래 반복단위 전체 중량에 대하여 0.5 내지 10 중량%로 포함되는 아크릴계 공중합체. The crosslinkable monomer-derived repeating unit is an acrylic copolymer containing 0.5 to 10% by weight based on the total weight of the repeating unit derived from the main monomer.
  7. 제1항에 있어서,The method of claim 1,
    상기 아크릴계 공중합체의 무늬 점도(ML1+4, 100 ℃)는 10 내지 70인 아크릴계 공중합체.The acrylic copolymer has a pattern viscosity (ML1+4, 100° C.) of 10 to 70.
  8. (메타)아크릴산 알킬 에스테르 단량체, (메타)아크릴산 알콕시 알킬 에스테르 단량체 및 가교성 단량체를 포함하는 주단량체 혼합물을 제조하는 단계; 및Preparing 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
    상기 주단량체 혼합물에 다관능성 단량체를 투입하고 중합하는 단계를 포함하고,Including the step of introducing and polymerizing a polyfunctional monomer to the main monomer mixture,
    다관능성 단량체는 상기 주단량체 혼합물 전체 100 중량부에 대하여 0.0005 내지 1 중량부로 투입되는 아크릴계 공중합체의 제조방법.The method for producing an acrylic copolymer in which 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.
  9. 제8항에 있어서,The method of claim 8,
    상기 다관능성 단량체는 상기 주단량체 혼합물 전체 100 중량부에 대하여 0.001 내지 0.05 중량부로 포함되는 아크릴계 공중합체의 제조방법.The method for producing an acrylic copolymer, wherein the polyfunctional monomer is contained in an amount of 0.001 to 0.05 parts by weight based on 100 parts by weight of the total of the main monomer mixture.
  10. 제1항 내지 제7항 중 어느 한 항에 따른 아크릴계 공중합체 및 충진제를 포함하는 아크릴계 공중합체 조성물.An acrylic copolymer composition comprising the acrylic copolymer and a filler according to any one of claims 1 to 7.
PCT/KR2020/011183 2019-10-11 2020-08-21 Acrylic copolymer, method for manufacturing same, and acrylic copolymer composition comprising same WO2021071085A1 (en)

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Publication number Priority date Publication date Assignee Title
JPH0615635B2 (en) * 1985-08-30 1994-03-02 日本合成ゴム株式会社 Novel rubber composition
JPH0739526B2 (en) * 1985-01-31 1995-05-01 日本合成ゴム株式会社 Vulcanized rubber composition
JP2005120143A (en) * 2003-10-14 2005-05-12 Jsr Corp Epoxy-group-containing rubber, its production method, its composition, and laminate
JP2015093926A (en) * 2013-11-12 2015-05-18 日油株式会社 Thermoplastic elastomer and thermoplastic resin composition
KR20190085931A (en) * 2016-11-30 2019-07-19 가부시키가이샤 오사카소다 Acrylic copolymer, and a crosslinked product thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0739526B2 (en) * 1985-01-31 1995-05-01 日本合成ゴム株式会社 Vulcanized rubber composition
JPH0615635B2 (en) * 1985-08-30 1994-03-02 日本合成ゴム株式会社 Novel rubber composition
JP2005120143A (en) * 2003-10-14 2005-05-12 Jsr Corp Epoxy-group-containing rubber, its production method, its composition, and laminate
JP2015093926A (en) * 2013-11-12 2015-05-18 日油株式会社 Thermoplastic elastomer and thermoplastic resin composition
KR20190085931A (en) * 2016-11-30 2019-07-19 가부시키가이샤 오사카소다 Acrylic copolymer, and a crosslinked product thereof

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