WO2019208821A1 - Procédé de production de caoutchouc acrylique, et caoutchouc acrylique obtenu par ce procédé - Google Patents

Procédé de production de caoutchouc acrylique, et caoutchouc acrylique obtenu par ce procédé Download PDF

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Publication number
WO2019208821A1
WO2019208821A1 PCT/JP2019/018096 JP2019018096W WO2019208821A1 WO 2019208821 A1 WO2019208821 A1 WO 2019208821A1 JP 2019018096 W JP2019018096 W JP 2019018096W WO 2019208821 A1 WO2019208821 A1 WO 2019208821A1
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Prior art keywords
acrylic rubber
weight
acid
producing
emulsion polymerization
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English (en)
Japanese (ja)
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文子 古国府
啓佑 小島
奨 佐藤
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Zeon Corp
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Zeon Corp
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Priority to SG11202010603TA priority Critical patent/SG11202010603TA/en
Priority to CN201980026455.1A priority patent/CN111989347B/zh
Priority to JP2019562016A priority patent/JP6708316B2/ja
Publication of WO2019208821A1 publication Critical patent/WO2019208821A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to a method for producing acrylic rubber, an acrylic rubber obtained by the production method, a rubber composition comprising the same, and a crosslinked rubber product obtained by crosslinking the rubber composition, and more particularly, storage stability.
  • the present invention relates to a method for producing an acrylic rubber excellent in the above, an acrylic rubber obtained by the production method, a rubber composition containing the same, and a rubber crosslinked product obtained by crosslinking the rubber composition.
  • Acrylic rubber is a polymer mainly composed of an acrylate ester and is generally known as a rubber excellent in heat resistance, oil resistance and ozone resistance, and is widely used in fields related to automobiles.
  • Such an acrylic rubber is usually obtained by emulsion polymerization of a monomer mixture constituting the acrylic rubber, coagulating the resulting emulsion polymerization solution by adding a coagulant, and drying the hydrous crumb obtained by coagulation.
  • a drying device such as a belt conveyor type band dryer or an extruder capable of drying in a continuous process is used.
  • the acrylic rubber produced in this way has a problem that problems such as Mooney scorch and burns occur during long-term storage.
  • the present invention has been made in view of such a situation, and an object of the present invention is to provide a method for producing an acrylic rubber capable of realizing excellent storage stability while maintaining good normal state physical properties.
  • the present inventors conducted emulsion polymerization by combining two specific emulsifiers in the method for producing acrylic rubber, and the resulting emulsion polymerization solution was obtained using a metal sulfate. It has been found that by washing and drying the water-containing crumb that can be solidified, an acrylic rubber that can realize excellent storage stability while maintaining good normal state properties can be produced.
  • the present inventors also have that the acrylic rubber has a crosslinkable functional group, uses a specific proportion of two types of emulsifiers and a redox polymerization catalyst as a polymerization initiator, particularly combines two specific types of reducing agents, Using at least one aspect of using a monovalent or divalent metal sulfate as a coagulant, and performing heating including contact with an emulsion polymerization solution and a metal sulfate to perform washing including acid washing By adopting it, it was found that the object of the present invention can be achieved to a higher degree, and the present invention has been completed.
  • At least one crosslinkable monomer selected from the group consisting of (meth) acrylic acid esters, carboxyl group-containing monomers, epoxy group-containing monomers, and halogen group-containing monomers.
  • An emulsion polymerization step for obtaining an emulsion polymerization solution by emulsion polymerization using a polymerization initiator in the presence of a nonionic emulsifier and an anionic emulsifier, and contacting the emulsion polymerization solution with a metal sulfate.
  • the ratio of the nonionic emulsifier to the anionic emulsifier is preferably in the range of 1/99 to 99/1 in terms of the weight ratio of the nonionic emulsifier / anionic emulsifier.
  • the use ratio of the nonionic emulsifier and the anionic emulsifier is in the range of 50/50 to 75/25 in terms of the weight ratio of the nonionic emulsifier / anionic emulsifier. preferable.
  • the polymerization initiator is preferably combined with a reducing agent.
  • a reducing agent In the method for producing acrylic rubber of the present invention, it is preferable to use at least two kinds of compounds as the reducing agent.
  • the metal ion-containing compound in the reduced state is preferably ferrous sulfate.
  • the reducing agent other than the metal ion-containing compound in the reduced state is preferably sodium formaldehyde sulfoxylate, ascorbic acid or ascorbate.
  • the reducing agent other than the metal ion-containing compound in the reduced state is preferably ascorbate.
  • the polymerization initiator is preferably an organic peroxide or an inorganic peroxide.
  • the contact between the emulsion polymerization solution and the metal sulfate is performed by adding the metal sulfate to the emulsion polymerization solution or by adding the emulsion polymerization solution to the gold sulfate of the genus sulfate. It is preferable to carry out by any method of charging into a solution or a dispersion.
  • the temperature at which the emulsion polymerization solution and the metal sulfate are in contact with each other is 60 ° C. or higher.
  • the metal sulfate is preferably a monovalent or divalent metal sulfuric acid solution.
  • the anionic emulsifier is preferably a phosphate ester salt.
  • the washing includes acid washing.
  • the acrylic rubber manufactured with the said manufacturing method is provided.
  • the monomer composition is 50 to 99.9% by weight of (meth) acrylate monomer units, 0.01 to 20% by weight of crosslinkable monomer units, and copolymerizable.
  • the other monomer units are preferably 0 to 49.99% by weight.
  • the Mooney viscosity (ML1 + 4, 100 ° C.) is preferably in the range of 10 to 150.
  • the rubber composition which contains the rubber component containing the said acrylic rubber and a crosslinking agent is provided.
  • the crosslinking agent includes a polyvalent amine compound, a polyvalent epoxy compound, a polyvalent carboxylic acid, an organic carboxylic acid ammonium salt, an organic carboxylic acid metal salt, an isocyanuric acid compound, a triazine compound, and a metal. It is preferably at least one selected from the group consisting of soap / sulfur.
  • the rubber composition of the present invention preferably further comprises a crosslinking accelerator.
  • the crosslinking accelerator includes a guanidine crosslinking accelerator, a diazabicycloalkene crosslinking accelerator, an aliphatic secondary amine crosslinking accelerator, an aliphatic tertiary amine crosslinking accelerator, and It is at least one selected from the group consisting of dithiocarbamate vulcanization accelerators.
  • the rubber composition of the present invention preferably further comprises a scorch inhibitor. In the rubber composition of this invention, it is preferable to mix
  • the rubber composition of the present invention preferably further contains a filler.
  • crosslinking the said rubber composition is provided.
  • an acrylic rubber capable of realizing excellent storage stability while maintaining normal physical properties, a rubber composition containing the same, and a rubber cross-linked product thereof.
  • the production method of the acrylic rubber of the present invention is (meth) acrylic acid ester [meaning acrylic acid ester and / or methacrylic acid ester. The same applies to methyl (meth) acrylate. And a nonionic emulsifier and an anion as a monomer comprising a carboxyl group-containing monomer, an epoxy group-containing monomer, and a halogen group-containing monomer.
  • a cleaning process for performing cleaning and a drying process for drying the cleaned water-containing crumb are provided.
  • the monomer used in the emulsion polymerization step of the present invention is characterized by having (meth) acrylic acid ester as a main component.
  • the (meth) acrylic acid ester as the main component is not particularly limited, and examples thereof include (meth) acrylic acid alkyl esters and (meth) acrylic acid alkoxyalkyl esters.
  • (meth) acrylic acid alkyl ester for example, an ester of an alkanol having 1 to 12 carbon atoms and (meth) acrylic acid is used, and an ester of an alkanol having 1 to 8 carbon atoms and (meth) acrylic acid is preferable. Further, an ester of alkanol having 2 to 6 carbon atoms and (meth) acrylic acid is more preferable.
  • ethyl (meth) acrylate and n-butyl (meth) acrylate are preferable.
  • Ethyl acrylate and n-butyl acrylate are particularly preferable.
  • the (meth) acrylic acid alkoxyalkyl ester is preferably an ester of an alkoxyalkyl alcohol having 2 to 12 carbon atoms and (meth) acrylic acid, specifically, methoxymethyl (meth) acrylate, (meth) Ethoxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, (meth) acrylic acid Examples thereof include 3-methoxypropyl and 4-methoxybutyl (meth) acrylate.
  • 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferred, 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are more preferred, and 2-methoxyethyl acrylate is preferred. Is more preferable.
  • the content of the (meth) acrylic acid ester in the monomer used for the polymerization is preferably the main component in the monomer, usually 50 to 99.9% by weight, preferably 60 to 99.7% by weight. More preferably, it is 70 to 99.5% by weight. If the content of (meth) acrylic acid ester is excessively small, the weather resistance, heat resistance, and oil resistance of the resulting rubber cross-linked product may be reduced. On the other hand, if the content is excessively large, Heat resistance may be reduced.
  • the (meth) acrylic acid ester is preferably composed of 30 to 100% by weight of (meth) acrylic acid alkyl ester and 70 to 0% by weight of (meth) acrylic acid alkoxyalkyl ester.
  • a crosslinkable monomer and another copolymerizable monomer can be contained.
  • the crosslinkable monomer is not particularly limited, and examples thereof include a carboxyl group-containing monomer, an epoxy group-containing monomer, a halogen atom-containing monomer, and a diene monomer, preferably a carboxyl group Containing monomers, epoxy group-containing monomers and halogen atom-containing monomers, more preferably halogen atom-containing monomers.
  • the carboxyl group-containing monomer is not particularly limited, but for example, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid can be suitably used.
  • ⁇ , ⁇ -ethylenically unsaturated carboxylic acid examples include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms, ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms, Examples thereof include monoesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms.
  • Use of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is preferred because it can further improve the compression set resistance when the resulting acrylic rubber is a rubber cross-linked product.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and cinnamic acid.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, citraconic acid and chloromaleic acid.
  • Examples of monoesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, and maleic acid.
  • Butenedionic acid mono-chain alkyl esters such as monomethyl, monoethyl maleate, mono-n-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleic acid Butenedionic acid monoesters having an alicyclic structure such as monocyclohexenyl; itaconic acid monoesters such as monomethyl itaconate, monoethyl itaconate, mono n-butyl itaconate, monocyclohexyl itaconate;
  • ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is preferable, and monoester of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms.
  • butenedionic acid mono-chain alkyl ester and butenedionic acid monoester having an alicyclic structure are particularly preferable.
  • Preferable specific examples include mono n-butyl fumarate, mono n-butyl maleate, monocyclohexyl fumarate, monocyclohexyl maleate and the like, and mono n-butyl fumarate is particularly preferred.
  • dicarboxylic acids include those that exist as anhydrides.
  • the epoxy group-containing monomer is not particularly limited.
  • an epoxy group-containing (meth) acrylate ester such as glycidyl (meth) acrylate
  • an epoxy group-containing styrene such as p-vinylbenzylglycidyl ether
  • Glycidyl ether and vinyl glycidyl ether 3,4-epoxy-1-pentene, 3,4-epoxy-1-butene, 4,5-epoxy-2-pentene, 4-vinylcyclohexyl glycidyl ether, cyclohexenylmethyl glycidyl ether
  • epoxy group-containing ethers such as 3,4-epoxy-1-vinylcyclohexene and allylphenyl glycidyl ether.
  • the halogen atom-containing monomer is not particularly limited.
  • unsaturated alcohol esters of halogen-containing saturated carboxylic acids (meth) acrylic acid haloalkyl esters, (meth) acrylic acid haloacyloxyalkyl esters, (meth) Examples include acrylic acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
  • Examples of the unsaturated alcohol ester of a halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
  • Examples of (meth) acrylic acid haloalkyl esters include chloromethyl (meth) acrylate, 1-chloroethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 1,2-dichloroethyl (meth) acrylate, Examples include 2-chloropropyl (meth) acrylate, 3-chloropropyl (meth) acrylate, and 2,3-dichloropropyl (meth) acrylate.
  • Examples of (meth) acrylic acid haloacyloxyalkyl esters include 2- (chloroacetoxy) ethyl (meth) acrylate, 2- (chloroacetoxy) propyl (meth) acrylate, and 3- (chloroacetoxy) (meth) acrylic acid. ) Propyl, 3- (hydroxychloroacetoxy) propyl (meth) acrylate, and the like.
  • Examples of (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl esters include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylate and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylate. It is done.
  • Examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether, and the like.
  • halogen-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone, and the like.
  • halomethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl- ⁇ -methylstyrene.
  • halogen-containing unsaturated amide examples include N-chloromethyl (meth) acrylamide.
  • haloacetyl group-containing unsaturated monomer examples include 3- (hydroxychloroacetoxy) propyl allyl ether, p-vinylbenzyl chloroacetate, and the like.
  • an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid is preferable, and vinyl chloroacetate (vinyl monochloroacetate) is more preferable.
  • crosslinkable monomers can be used alone or in combination of two or more.
  • the content of the crosslinkable monomer in the monomer is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
  • the mechanical properties and the compression set resistance when the resulting acrylic rubber is used as a crosslinked product can be highly balanced.
  • Other monomers that can be copolymerized are not particularly limited as long as they can be copolymerized, and examples thereof include aromatic vinyl monomers, ⁇ , ⁇ -ethylenically unsaturated nitrile monomers, and acrylamide monomers. And other olefinic monomers.
  • aromatic vinyl monomer include styrene, ⁇ -methylstyrene, divinylbenzene, and the like.
  • ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
  • acrylamide monomers include acrylamide and methacrylamide.
  • Examples of other olefinic monomers include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, butyl vinyl ether, and the like.
  • these other copolymerizable monomers styrene, acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are preferable, and acrylonitrile, methacrylonitrile and ethylene are more preferable.
  • These other copolymerizable monomers can be used alone or in combination of two or more.
  • the content of these other copolymerizable monomers in the monomer is usually 49.99% by weight or less, preferably 39.9% by weight or less, more preferably 29.5% by weight or less.
  • the monomer having the (meth) acrylic acid ester as a main component is emulsion-polymerized using a polymerization initiator in the presence of a nonionic emulsifier and an anionic emulsifier to obtain an emulsion polymerization solution. It is characterized by that.
  • the nonionic emulsifier is not particularly limited, and examples thereof include polyoxyalkylene alkyl ethers such as polyoxyethylene dodecyl ether; polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene stearic acid esters and the like. Oxyalkylene fatty acid ester; polyoxyethylene sorbitan alkyl ester; polyoxyethylene / polyoxypropylene copolymer; and the like.
  • polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene / polyoxypropylene copolymer, and the like are preferable, and polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene / polyethylene are particularly preferable.
  • Oxypropylene copolymers are preferred.
  • the weight average molecular weight of the nonionic emulsifier is not particularly limited, but is usually in the range of 300 to 50,000, preferably 500 to 30,000, more preferably 1,000 to 15,000. These nonionic emulsifiers can be used alone or in combination of two or more.
  • the anionic emulsifier is not particularly limited, and examples thereof include salts of fatty acids such as myristic acid, palmitic acid, oleic acid, and linolenic acid; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; higher alcohols such as sodium lauryl sulfate.
  • Phosphate ester salts such as sulfate ester salts and sodium alkyl phosphate esters, preferably higher alcohol phosphate ester salts such as sodium phosphate ester alcohols having a hydrophobic group with 6 or more carbon atoms; alkyl sulfosuccinates and the like it can.
  • anionic emulsifiers phosphate ester salts and higher alcohol sulfate ester salts are preferable, higher alcohol phosphate ester salts and higher alcohol sulfate ester salts are more preferable, and higher alcohol phosphate ester salts are more preferable.
  • anionic emulsifiers can be used alone or in combination of two or more.
  • the use ratio of the nonionic emulsifier and the anionic emulsifier is usually 1/99 to 99/1, preferably 10/90 to 80/20, more preferably 25/75, in a weight ratio of nonionic emulsifier / anionic emulsifier.
  • the range is from 75/25, more preferably from 50/50 to 75/25, and most preferably from 65/35 to 75/25.
  • the amount of sulfate used it is possible to reduce the amount of sulfate used, and as a result, the amount of coagulant in the finally obtained acrylic rubber can be reduced, thereby improving the water resistance of the resulting rubber cross-linked product. it can.
  • the ratio of the nonionic emulsifier and the anionic emulsifier within this range, the emulsifying action can be enhanced, so that the amount of the emulsifier itself can be reduced, and finally obtained as a result.
  • the residual amount of the emulsifier contained in the acrylic rubber can be reduced, which is preferable because the water resistance of the resulting acrylic rubber can be further increased.
  • the amount of the emulsifier used is generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on the total amount of the emulsifier used with respect to 100 parts by weight of the monomer used for the polymerization. Range.
  • emulsifiers can be used as an emulsifier, if necessary.
  • examples of other emulsifiers include cationic emulsifiers, and specific examples include alkyltrimethylammonium chloride, dialkylammonium chloride, and benzylammonium chloride. These other emulsifiers can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the object of the present invention.
  • azo compounds such as azobisisobutyronitrile; organic peroxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, benzoyl peroxide; sodium persulfate, persulfate Inorganic peroxides such as potassium, hydrogen peroxide, and ammonium persulfate; can be used.
  • organic peroxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, benzoyl peroxide
  • sodium persulfate persulfate
  • persulfate Inorganic peroxides such as potassium, hydrogen peroxide, and ammonium persulfate
  • an organic peroxide and / or an inorganic peroxide is used as a polymerization initiator, it is preferably used as a redox polymerization initiator in combination with a reducing agent.
  • a metal ion containing compound in a reduced state such as ferrous sulfate, sodium hexamethylenediamine tetraacetate, cuprous naphthenate; Ascorbic acid, sodium ascorbate, ascorbine Ascorbic acid (salt) such as potassium acid; erythorbic acid (salt) such as erythorbic acid, sodium erythorbate, potassium erythorbate; saccharides; sulfinates such as sodium hydroxymethanesulfinate; sodium sulfite, potassium sulfite, sodium bisulfite Sodium aldehyde, sodium bisulfite, potassium bisulfite; pyrosulfites such as sodium
  • reducing agents can be used singly or in combination of two or more, but are preferably used in combination of two or more, more preferably containing metal ions in a reduced state as the first reducing agent.
  • Combining the compound with a reducing agent other than the metal ion-containing compound in the reduced state as the second reducing agent more preferably combining ferrous sulfate with ascorbic acid (salt) and / or sodium formaldehyde sulfoxylate
  • the object of the present application can be achieved to a higher degree by combining with ferrous sulfate and ascorbate.
  • the amount of the reducing agent used is preferably in the range of 0.0001 to 0.5 parts by weight as a total amount with respect to 100 parts by weight of the monomer used for the polymerization.
  • the amount of water used is preferably 80 to 500 parts by weight, more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • polymerization auxiliary materials such as a molecular weight adjusting agent, a particle size adjusting agent, a chelating agent, and an oxygen scavenger can be used as necessary.
  • the emulsion polymerization may be carried out by any of batch, semi-batch and continuous methods, but the semi-batch method is preferred. Specifically, in the reaction system containing the polymerization initiator and the reducing agent, the polymerization reaction is performed while continuously dropping the monomers used for the polymerization to the polymerization reaction system from the start of the polymerization reaction to an arbitrary time.
  • the polymerization reaction is preferable to perform the polymerization reaction while continuously dropping into the polymerization reaction system from the start of the polymerization reaction to any time, It is more preferable to perform the polymerization reaction while continuously dropping the monomer, polymerization initiator, and reducing agent used for the polymerization from the start of the polymerization reaction to an arbitrary time while continuously dropping into the polymerization reaction system.
  • the polymerization is usually performed in a temperature range of 0 to 70 ° C., preferably 5 to 50 ° C.
  • the monomer used for polymerization is mixed with an emulsifier and water to obtain a monomer emulsion (preparation of emulsion).
  • Step) it is preferable to continuously drop in the state of a monomer emulsion.
  • the method for preparing the monomer emulsion is not particularly limited, and includes a method of stirring the total amount of monomers used for polymerization, the total amount of emulsifier, and water using a stirrer such as a homomixer or a disk turbine. Can be mentioned.
  • the amount of water used in the monomer emulsion is preferably 10 to 70 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • the polymerization reaction when the polymerization reaction is carried out while continuously dropping into the polymerization reaction system from the start of the polymerization reaction to an arbitrary time for all of the monomer, polymerization initiator, and reducing agent used for the polymerization, these are separate. Or at least the polymerization initiator and the reducing agent may be mixed in advance and, if necessary, dropped into the polymerization system from the same dropping device as an aqueous solution. May be. After completion of dropping, the reaction may be continued for an arbitrary time in order to further improve the polymerization reaction rate.
  • the completion of emulsion polymerization can be performed by adding a polymerization terminator as necessary.
  • the polymerization terminator include hydroxylamine, hydroxyamine sulfate, diethylhydroxyamine, hydroxyaminesulfonic acid and its alkali metal salt, sodium dimethyldithiocarbamate, hydroquinone and the like.
  • the amount of the polymerization terminator used is not particularly limited, but is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • various compounding agents can be added to the pre-coagulation emulsion polymerization solution obtained by emulsion polymerization, if necessary, and uniformly dispersed in the produced acrylic rubber polymer.
  • the compounding agent to be added is not particularly limited as long as it is a compounding agent for rubber.
  • an antiaging agent, a lubricant, an alkylene oxide polymer, and the like can be effectively blended, and are suitable.
  • an anti-aging agent in the emulsion polymerization liquid before coagulation, deterioration of the acrylic rubber due to heat during drying in the drying step described later can be effectively suppressed. Specifically, it is possible to effectively suppress a decrease in Mooney viscosity due to deterioration due to heating during drying, thereby effectively reducing the normal tensile strength and elongation at break when a rubber cross-linked product is obtained. It can be raised.
  • the anti-aging agent in the state of the emulsion polymerization liquid before coagulation, by blending the anti-aging agent, the anti-aging agent can be appropriately dispersed, so even when the amount of the anti-aging agent is reduced, The effect of addition can be sufficiently exhibited.
  • the blending amount of the antioxidant is preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1.2 parts by weight with respect to 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid. Even when the amount is relatively small, the effect of the addition can be sufficiently exhibited. Even when the anti-aging agent is contained in the emulsion polymerization solution before coagulation, the added anti-aging agent is not substantially removed in the subsequent coagulation, washing, drying, etc. The effect of the addition can be sufficiently exhibited.
  • a method of containing an anti-aging agent in an emulsion polymerization solution a method of adding to an emulsion polymerization solution after emulsion polymerization and before coagulation, or a method of adding to a solution before emulsion polymerization is performed
  • a method of adding to an emulsion polymerization solution after emulsion polymerization and before coagulation or a method of adding to a solution before emulsion polymerization is performed
  • aggregates may be generated during emulsion polymerization, which may cause contamination of the polymerization apparatus.
  • the method of adding to the emulsion polymerization liquid before coagulating is more preferable.
  • the anti-aging agent is not particularly limited.
  • 2,6-di-t-butyl-4-methylphenol 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-
  • 2,6-di-t- Such as butyl- ⁇ -dimethylamino-p-cresol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, mono (or di- or tri) ( ⁇ -methylbenzyl) phenol, etc.
  • the lubricant is not particularly limited.
  • hydrocarbon lubricants such as liquid paraffin, paraffin wax and synthetic polyethylene wax
  • fatty acid ester lubricants such as stearic acid alkyl ester
  • Fatty acid amide type lubricants such as calcium stearate, magnesium stearate, zinc stearate and other metal soap type lubricants
  • polyoxyethylene stearyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxy And phosphoric acid ester lubricants such as polyoxyethylene higher alcohol phosphoric acid such as ethylene tridecyl ether phosphoric acid
  • higher fatty acid lubricants such as fatty acids having 10 to 30 carbon atoms, preferably 12 to 20 carbon atoms; .
  • fatty acid ester-based, fatty acid amide-based, phosphate ester-based, and higher fatty acid-based lubricants preferably phosphate ester-based lubricants and higher fatty acid-based lubricants, more preferably polyoxyethylene stearyl ether phosphoric acid.
  • the acrylic rubber to be produced is suitable because it is highly improved in handling and roll processability when dried.
  • lubricants can be used alone or in combination of two or more, and the amount added is appropriately selected according to the purpose of use, but is 100 parts by weight of the acrylic rubber component contained in the emulsion polymerization liquid. On the other hand, it is usually in the range of 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight.
  • the lubricant By preliminarily containing the lubricant in the emulsion polymerization liquid before coagulation, the lubricant can be favorably dispersed in the emulsion polymerization liquid before coagulation.
  • the lubricant can be contained in a well dispersed state.
  • it is possible to appropriately include a lubricant preferably, it can be included in a uniformly dispersed state), whereby the resulting acrylic rubber, It can be made excellent in handling at the time of drying and roll processability. Even when the lubricant is contained in the emulsion polymerization solution before coagulation, the added lubricant is not substantially removed in the subsequent coagulation, washing, drying, etc. It can be fully demonstrated.
  • the alkylene oxide polymer is not particularly limited as long as it is an alkylene oxide polymer, but a lower alkylene oxide polymer is usually used. Specific examples include polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide copolymer, and among these, polyethylene oxide is preferable.
  • the weight average molecular weight of the alkylene oxide polymer is selected according to the purpose of use, but is usually 10,000 to 6,000,000, preferably 30,000 to 1,000,000, more preferably 50,000. It is in the range of ⁇ 500,000, particularly preferably 50,000 to 300,000, most preferably 80,000 to 200,000. When the weight average molecular weight of the alkylene oxide polymer is in this range, the object of the present invention can be achieved to a high degree, which is preferable.
  • alkylene oxide polymers can be used alone or in combination of two or more, and the blending amount is preferably 0.01 with respect to 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid.
  • the range is from 1 to 1 part by weight, more preferably from 0.01 to 0.6 part by weight, still more preferably from 0.02 to 0.5 part by weight.
  • the coagulation step of the present invention is characterized in that the emulsion polymerization solution to which an antiaging agent, a lubricant and / or an alkylene oxide polymer is added as necessary is brought into contact with a metal sulfate to coagulate to obtain a hydrous crumb. To do.
  • the metal sulfate used as the coagulant is not particularly limited.
  • a monovalent to trivalent metal sulfate can be preferably used, and a monovalent or divalent metal sulfate is more preferable.
  • Specific examples include sodium sulfate, potassium sulfate, lithium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate, titanium sulfate, manganese sulfate, iron sulfate, cobalt sulfate, nickel sulfate, aluminum sulfate, tin sulfate, and the like.
  • Sodium sulfate, magnesium sulfate, and aluminum sulfate are preferable, and sodium sulfate and magnesium sulfate are more preferable.
  • metal sulfates can be used alone or in combination of two or more.
  • the amount of the metal sulfate used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid. Range. When the metal sulfate is in this range, it is possible to achieve a high balance between compression set resistance, water resistance and storage stability when the acrylic rubber is crosslinked while sufficiently solidifying the acrylic rubber. It is.
  • other coagulants can be used in combination with the metal sulfate as necessary.
  • other coagulants include metals such as sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, zinc chloride, titanium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, aluminum chloride, and tin chloride.
  • Chlorides such as sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, zinc nitrate, titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, aluminum nitrate, tin nitrate;
  • metal nitrates such as sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, zinc nitrate, titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, aluminum nitrate, tin nitrate;
  • the method of bringing the emulsion polymerization solution into contact with the metal sulfate may be in accordance with a conventional method.
  • a metal sulfate or a solution or dispersion of metal sulfate is added to the emulsion polymerization solution, or the emulsion polymerization solution is added to the metal sulfate. It can be carried out by putting it in a solution or dispersion.
  • an aqueous solution is usually used, and the concentration of the metal sulfate in the aqueous solution is appropriately selected according to the purpose of use, and is usually 1 to 50% by weight.
  • the range is preferably 5 to 40% by weight, more preferably 10 to 30% by weight.
  • the contact (coagulation) temperature between the emulsion polymerization solution and the metal sulfate is not particularly limited, but is usually 60 ° C. or higher, preferably 65 to 100 ° C., more preferably 70 to 95 ° C., and still more preferably 78 to 95 ° C., most preferably in the range of 83-95 ° C.
  • the washing process of the present invention is to wash the water-containing crumb obtained in the above-described coagulation process.
  • the washing method is not particularly limited, and examples thereof include a method of washing with water by using water as a washing liquid and mixing the added water together with the hydrated crumb.
  • the temperature at the time of washing with water is not particularly limited, but is preferably 5 to 60 ° C., more preferably 10 to 50 ° C., and the mixing time is 1 to 60 minutes, more preferably 2 to 30 minutes.
  • the amount of water to be added to the hydrated crumb at the time of washing with water is not particularly limited, but from the viewpoint that the residual amount of coagulant in the finally obtained acrylic rubber can be effectively reduced,
  • the amount of water per washing is preferably 50 to 9,800 parts by weight, more preferably 300 to 1,800 parts per 100 parts by weight of the solid content (mainly acrylic rubber component) contained in the hydrous crumb. Parts by weight.
  • the number of times of washing with water is not particularly limited, and may be one. However, it is preferably performed a plurality of times from the viewpoint of reducing the residual amount of coagulant in the finally obtained acrylic rubber, and preferably 2 to 10 times. More preferably, it is 3 to 8 times. In addition, from the viewpoint of reducing the residual amount of coagulant in the finally obtained acrylic rubber, it is desirable that the number of times of washing with water is large, but even if the washing exceeds the above range, the coagulant removing effect is effective. On the other hand, it is preferable that the number of washings is in the above range because the influence of the decrease in productivity is increased by increasing the number of steps.
  • acid washing using an acid as a washing solution may be performed.
  • acid cleaning By carrying out the acid cleaning, the storage stability of the acrylic rubber can be enhanced to a high level, and the compression set resistance in the case of a rubber cross-linked product can also be improved.
  • the acid used for the acid cleaning is not particularly limited, and sulfuric acid, hydrochloric acid, phosphoric acid and the like can be used without limitation.
  • the acid washing method is not particularly limited, and examples thereof include a method of mixing an aqueous solution of the added acid together with water-containing crumb.
  • the temperature during the acid cleaning is not particularly limited, but is preferably 5 to 60 ° C., more preferably 10 to 50 ° C., and the mixing time is 1 to 60 minutes, more preferably 2 to 30 minutes.
  • the pH of the acid-washed wash water can be determined, for example, by measuring the pH of the water contained in the hydrous crumb after the acid wash.
  • the water washing conditions may be the same as those described above.
  • the water-containing crumb may be filtered using a sieve such as a rotary screen or a vibrating screen; a centrifugal dehydrator;
  • the drying temperature in the drying step is not particularly limited and varies depending on the dryer used for drying.
  • the drying temperature is preferably 80 to 200 ° C., 100 More preferably, the temperature is set to ⁇ 170 ° C.
  • the acrylic rubber of the present invention can be obtained by the above production method.
  • the acrylic rubber of the present invention thus obtained has excellent storage stability while maintaining good normal state properties.
  • the acrylic rubber of the present invention is not particularly limited except that it contains a (meth) acrylic acid ester monomer unit as a main component. However, when it further contains a crosslinkable monomer unit, the effect of the present invention is enhanced to a high degree. Is preferable.
  • the monomer composition in the acrylic rubber of the present invention is appropriately selected according to the purpose of use, but the (meth) acrylic acid ester monomer unit is usually 50 to 99.9% by weight, preferably 60 to 99. 0.7 wt%, more preferably 70 to 99.5 wt%, and the content of the crosslinkable monomer unit is usually 0.01 to 20 wt%, preferably 0.1 to 10 wt%, more preferably Is 0.5 to 5% by weight, and the content of other copolymerizable monomer units is usually 0 to 49.99% by weight, preferably 0 to 39.9% by weight, more preferably 0 ⁇ 29.5% by weight.
  • Examples of the (meth) acrylic acid ester monomer, the crosslinkable monomer, and other copolymerizable monomers are the same as those exemplified in the above ⁇ Monomer>.
  • Examples of the crosslinkable monomer unit include a carboxyl group-containing monomer unit, a halogen group-containing monomer unit, and an epoxy group-containing monomer unit, and a halogen group-containing monomer unit is preferable.
  • the Mooney viscosity (ML1 + 4, 100 ° C.) of the acrylic rubber of the present invention is selected according to the purpose of use, but is usually in the range of 10 to 150, preferably 20 to 100, more preferably 25 to 60.
  • the glass transition temperature (Tg) of the acrylic rubber of the present invention is selected according to the purpose of use, but is usually 15 ° C. or lower, preferably 0 ° C. or lower.
  • the manufacturing method of such an acrylic rubber and the acrylic rubber obtained by this manufacturing method are provided.
  • the acrylic rubber of the present invention obtained by the above production method it has excellent storage stability while maintaining good normal state physical properties.
  • rubber such as acrylic rubber
  • it is normal to coagulate when obtaining a solid rubber from a solution or dispersion of a rubber obtained by polymerization, according to the knowledge of the present inventors.
  • the characteristic of the acrylic rubber obtained changes greatly with the state at the time of solidification.
  • the acrylic rubber of the present invention performs such coagulation using a metal sulfate as a coagulant.
  • a metal sulfate as a coagulant.
  • a nonionic emulsifier and an anionic emulsifier are also included during coagulation.
  • the acrylic rubber obtained by such coagulation contains a metal sulfate, a nonionic emulsifier and an anionic emulsifier as a coagulant.
  • the acrylic rubber contains In addition, the inclusion of a metal sulfate, a nonionic emulsifier, and an anionic emulsifier does not produce an effect that storage stability can be improved while maintaining normal physical properties, and emulsion polymerization. It has been found that it is necessary to use a nonionic emulsifier and an anionic emulsifier sometimes, and at the time of coagulation, using a metal sulfate as a coagulant.
  • the acrylic rubber of the present invention can be obtained for the first time through such a process, and can be specified simply by the words that it contains a metal sulfate, a nonionic emulsifier and an anionic emulsifier. It is not possible.
  • the rubber composition of the present invention comprises a rubber component containing the acrylic rubber and a crosslinking agent.
  • the content of the acrylic rubber of the present invention in the rubber component may be selected according to the purpose of use, for example, usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more. Particularly preferred is 100% by weight.
  • the above acrylic rubber can be used alone or in combination with the above acrylic rubber and other rubbers.
  • Other rubbers include acrylic rubbers other than the acrylic rubber of the present invention, natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silicon rubber, fluorine rubber, olefin elastomer, styrene elastomer, Examples include vinyl chloride elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers, polysiloxane elastomers, and the like.
  • the content of other rubbers in the rubber component is appropriately selected within a range not impairing the effects of the present invention, and is usually 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less.
  • crosslinking agent used for the rubber composition of this invention
  • diamine compound polyvalent amine compounds, such as dithiocarbamic acid, and its carbonate
  • Sulfur compound Sulfur donor
  • Conventionally known crosslinking agents such as compounds; organic carboxylic acid ammonium salts; polyvalent carboxylic acids; isocyanuric acid compounds; organic peroxides; triazine compounds;
  • polyvalent amine compounds and triazine compounds are preferable, and triazine compounds are particularly preferable.
  • polyvalent amine compound examples include aliphatic polyvalent amine compounds such as hexamethylene diamine, hexamethylene diamine carbamate, N, N′-dicinnamylidene-1,6-hexane diamine; 4,4′-methylene dianiline, p.
  • hexamethylenediamine carbamate 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, and the like are preferable.
  • These polyvalent amine compounds are particularly preferably used in combination with a carboxyl group-containing acrylic rubber (an acrylic rubber containing a carboxyl group-containing monomer unit as a crosslinkable monomer unit).
  • triazine compound examples include 6-trimercapto-s-triazine, 2-anilino-4,6-dithiol-s-triazine, 1-dibutylamino-3,5-dimercaptotriazine, 2-dibutylamino-4, 6-dithiol-s-triazine, 1-phenylamino-3,5-dimercaptotriazine, 2,4,6-trimercapto-1,3,5-triazine, 1-hexylamino-3,5-dimercaptotriazine Etc.
  • These triazine compounds are particularly preferably used in combination with a halogen group-containing acrylic rubber (acrylic rubber containing a halogen group-containing monomer unit as a crosslinkable monomer unit).
  • Examples of the organic carboxylic acid ammonium salt include ammonium benzoate and ammonium adipate; examples of the dithiocarbamic acid compound include dimethyldithiocarbamic acid and zinc dimethyldithiocarbamate; examples of the polyvalent carboxylic acid include tetradecanoic acid and isocyanuric acid. Examples of the compound include isocyanuric acid and isocyanuric acid ammonium.
  • ammonium benzoate, dimethyldithiocarbamic acid, and isocyanuric acid are particularly suitable in combination with an epoxy group-containing acrylic rubber (an acrylic rubber containing an epoxy group-containing monomer unit as a crosslinkable monomer unit). Used for.
  • crosslinking agents can be used alone or in combination of two or more kinds, and the blending amount is usually 0.001 to 20 parts by weight, preferably 0.1 to 20 parts by weight per 100 parts by weight of the rubber component.
  • the amount is 10 parts by weight, more preferably 0.1 to 5 parts by weight.
  • the rubber composition of the present invention is preferable because it can further improve the effects of the present invention by further blending a crosslinking accelerator.
  • a crosslinking accelerator for example, a guanidine type crosslinking accelerator, a diazabicycloalkene type crosslinking accelerator, an aliphatic secondary amine type crosslinking accelerator, an aliphatic tertiary amine type crosslinking accelerator, dithiocarbamic acid Suitable examples include salt-based vulcanization accelerators.
  • guanidine-based crosslinking accelerators and dithiocarbamate-based crosslinking accelerators are particularly preferable, and dithiocarbamate-based crosslinking accelerators are more preferable.
  • guanidine accelerators include 1,3-diphenylguanidine (DPG), 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, dicatecholborate di-o-tolylguanidine. 1,3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine, and the like.
  • DPG 1,3-diphenylguanidine
  • 1,3-di-o-tolylguanidine 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, dicatecholborate di-o-tolylguanidine.
  • 1,3-diphenylguanidine 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide are preferred because of their high reactivity, and 1,3-diphenylguanidine (DPG) is particularly preferred because of their higher reactivity.
  • diazabicycloalkene vulcanization accelerator examples include 1,8-diazabicyclo [5.4.0] unde-7-cene, 1,5-diazabicyclo [4.3.0] no-5-ene. And so on.
  • Examples of the aliphatic secondary amine vulcanization accelerator include dimethylamine, diethylamine, dipropylamine, diallylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-sec-butylamine, dihexylamine, Diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dicetylamine, di-2-ethylhexylamine, dioctadecylamine it can.
  • Examples of the aliphatic tertiary amine vulcanization accelerator include trimethylamine, triethylamine, tripropylamine, triallylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, tri-sec-butylamine, and trihexyl.
  • Examples include amine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, triundecylamine, and tridodecylamine.
  • dithiocarbamate vulcanization accelerator examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, N-ethyl -Zinc N-phenyldithiocarbamate, zinc dibenzyldithiocarbamate, copper dipropyldithiocarbamate, copper diisopropyldithiocarbamate, copper dibutyldithiocarbamate, sodium diethyldithiocarbamate, sodium diisopropyldithiocarbamate, sodium dibutyldithiocarbamate, dimethyldithiocarbamate
  • examples thereof include iron and ferric diethyldithiocarbamate.
  • zinc dimethyldithiocarbamate zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate and the like are preferable.
  • crosslinking accelerator used in the present invention other crosslinking accelerators other than the above can be used.
  • crosslinking accelerators include N-cyclohexyl-2-benzothiazylsulfenamide, N-tert-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N.I.
  • Sulfenamide vulcanization accelerators such as N-diisopropyl-2-benzothiazole sulfenamide; thiourea vulcanization accelerators such as diethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc Thiazole vulcanization accelerators such as salts; xanthogenic acid vulcanization accelerators such as sodium isopropylxanthate, zinc isopropylxanthate, and zinc butylxanthate; thiuram vulcanizations such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide Accelerators; Imidazole vulcanization accelerators such as 2-methylimidazole and 2-phenylimidazole; tetra n-butylammonium bromide, octadecyltri-n-butylammoni
  • crosslinking accelerators can be used singly or in combination of two or more, and the blending amount thereof is usually 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the rubber component. 1 to 10 parts by weight, more preferably 1 to 5 parts by weight. When the content of the crosslinking accelerator is within this range, it is preferable because the tensile strength and compression set resistance of the resulting rubber crosslinked product can be further improved.
  • the rubber composition of the present invention is preferable because the cross-linking properties are improved by further blending a scorch inhibitor.
  • the scorch inhibitor is not particularly limited, and examples thereof include imide compounds such as N-cyclohexylthiophthalimide, alkylamine alkylphenol compounds, hydroquinone / quinone compounds, and 2,4-di (3-isopropylphenyl) -4-methyl. -1-pentene can be mentioned, and an imide compound is preferable.
  • scorch preventing agents can be used alone or in combination of two or more, and the blending amount is 0.01 to 5 parts by weight, preferably 0.05 to 100 parts by weight of the rubber component.
  • the range is from 1 to 1 part by weight, more preferably from 0.1 to 0.5 part by weight.
  • the rubber composition of the present invention preferably further contains a filler.
  • a filler there is no special limitation as a filler, For example, a reinforcing filler, a non-reinforcing filler, etc. are mentioned, Preferably it is a reinforcing filler.
  • Examples of the reinforcing filler include carbon black such as furnace black, acetylene black, thermal black, channel black, and graphite; silica such as wet silica, dry silica, colloidal silica, and the like.
  • Non-reinforcing fillers include quartz powder, diatomaceous earth, zinc white, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, aluminum sulfate, calcium sulfate, and barium sulfate. be able to.
  • fillers can be used alone or in combination of two or more, and the blending amount is appropriately selected within a range not impairing the effects of the present invention, and is usually based on 100 parts by weight of the rubber component.
  • the range is 1 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight.
  • the rubber composition of the present invention may further contain a silane coupling agent.
  • the silane coupling agent that can be used is not particularly limited.
  • silane coupling agents can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected according to the purpose of use, and is usually 0.
  • the range is 01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight.
  • the rubber composition of the present invention may contain the above crosslinking agent and other compounding agents other than the crosslinking accelerator, scorch inhibitor, filler and silane coupling agent used as necessary.
  • Other compounding agents include, for example, dispersants such as higher fatty acids and their metal amine salts, plasticizers such as phthalic acid derivatives, adipic acid derivatives and sebacic acid derivatives, lubricating oils, process oils, coal tar, castor oil, Softener such as calcium stearate, anti-aging agent, light stabilizer, processing aid, adhesive, lubricant, flame retardant, anti-mold agent, antistatic agent, colorant, crosslinking retarder, polyolefin resin, polystyrene resin, Examples include polyacrylic resins, polyphenylene ether resins, polyester resins, polycarbonate resins, polyamide resins, vinyl chloride resins, and fluororesins. These other compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected
  • the blending procedure may be a normal procedure performed in the field of polymer processing, for example, a component that is not easily reacted or decomposed by heat and then easily reacted or decomposed by heat. It is preferable to mix a crosslinking agent or the like in a short time at a temperature at which no reaction or decomposition occurs.
  • the rubber cross-linked product of the present invention is obtained by cross-linking the rubber composition.
  • the rubber cross-linked product of the present invention uses the rubber composition of the present invention and is molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, and a roll, and heated. It can be produced by carrying out a cross-linking reaction and fixing the shape as a rubber cross-linked product. In this case, crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 150 ° C.
  • the crosslinking temperature is usually 100 to 250 ° C., preferably 130 to 220 ° C., more preferably 150 to 200 ° C.
  • the crosslinking time is usually 0.1 minutes to 10 hours, preferably 1 minute to 5 hours.
  • a heating method a method used for crosslinking of rubber, such as press heating, steam heating, oven heating, and hot air heating, may be appropriately selected.
  • the rubber cross-linked product of the present invention may be further heated and subjected to secondary cross-linking depending on the shape and size of the rubber cross-linked product.
  • the secondary crosslinking varies depending on the heating method, crosslinking temperature, shape, etc., but is preferably performed for 1 to 48 hours. What is necessary is just to select a heating method and heating temperature suitably.
  • the crosslinked rubber product of the present invention has excellent compression set resistance while maintaining the basic properties of rubber such as tensile strength, elongation, and hardness.
  • the compression set measured according to JIS K6262 of the rubber cross-linked product of the present invention is appropriately selected depending on the intended use, but is usually 1 to 50%, preferably 5 to 25%, more preferably 8 It is in the range of ⁇ 20%.
  • the rubber cross-linked product of the present invention makes use of the above characteristics, for example, O-ring, packing, diaphragm, oil seal, shaft seal, bearing seal, mechanical seal, well head seal, electrical / electronic device seal, air compression Sealing materials such as equipment seals; rocker cover gaskets attached to the connecting part between the cylinder block and the cylinder head, oil pan gaskets attached to the connecting part between the oil pan and the cylinder head or transmission case, positive electrode, electrolyte plate, Various gaskets such as a gasket for a fuel cell separator and a gasket for a top cover of a hard disk drive mounted between a pair of housings sandwiching a unit cell equipped with a negative electrode; a cushioning material, a vibration isolating material; a wire covering material; an industrial belt; Tubes and hoses; sea It is suitably used as such; s.
  • the rubber cross-linked product of the present invention is a fuel oil around a fuel tank such as a fuel hose, filler neck hose, vent hose, paper hose, oil hose, etc. It is suitably used for various hoses such as air hoses such as system hoses, turbo air hoses and emission control hoses, radiator hoses, heater hoses, brake hoses and air conditioner hoses.
  • Mooney viscosity (ML1 + 4, 100 ° C.) The Mooney viscosity (polymer Mooney) of the acrylic rubber was measured according to JIS K6300.
  • Mooney scorch test (ML145 ° C)
  • the Mooney scorch time (t5 and t35) and Vmin of the acrylic rubber composition were measured at 145 ° C. according to JIS K6300.
  • the time when the Mooney viscosity increased 5M from Vmin was defined as t5
  • the time when the Mooney viscosity increased 35M from Vmin was defined as t35.
  • the acrylic rubber composition used for the measurement was prepared according to JIS K6299.
  • t5 and t35 mean that the larger the value, the longer it takes to vulcanize, and it can be judged that the storage stability of the rubber composition is excellent, and the effect of promoting vulcanization is suppressed (well controlled). .
  • Vmin means that the lower the value, the less the initial vulcanization of the rubber composition, and it can be judged that the storage stability is excellent.
  • a Mooney scorch test Mooney scorch test after storage
  • Vmin of the Mooney scorch test before storage was defined as ⁇ Vmin. It can be judged that the smaller the value of ⁇ Vmin, the smaller the change in the rubber composition during storage, and the better the storage stability.
  • compression set test The acrylic rubber composition is molded and crosslinked by pressing at 170 ° C. for 20 minutes to produce a cylindrical specimen having a diameter of 29 mm and a thickness of 12.5 mm, and further heated at 150 ° C. for 4 hours for secondary crosslinking. I let you. According to JIS K6262, the test piece after secondary crosslinking obtained above was allowed to stand in an environment of 150 ° C. for 70 hours while being compressed at 25%, and then released from compression to give a compression set (% ) Was measured. It shows that it is excellent in compression set resistance property, so that the value of compression set rate (%) is small.
  • Example 1 In a mixing vessel equipped with a homomixer, 49.95 parts pure water, 40.9 parts ethyl acrylate, 35.0 parts n-butyl acrylate, 20.0 parts 2-methoxyethyl acrylate, 1.5 parts acrylonitrile , 2.6 parts of monochlorovinyl acetate, 0.57 parts of sodium lauryl sulfate (trade name “Emar 2FG”, manufactured by Kao Corporation) as an anionic emulsifier, and a polyoxyethylene / polyoxypropylene copolymer as a nonionic emulsifier A monomer emulsion was obtained by stirring 1.40 parts (trade name “Pronon 208”, manufactured by NOF Corporation) and 0.22 part of sodium L-ascorbate.
  • reaction was continued for 1 hour while maintaining the temperature in the polymerization reaction vessel at 23 ° C., and it was confirmed that the polymerization conversion rate reached 95%, and polymerization was carried out by adding hydroquinone as a polymerization terminator. The reaction was stopped to obtain an emulsion polymerization solution.
  • Mono (or di or tri) ( ⁇ -methylbenzyl) phenol (trade name “NOCRACK SP”, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as an anti-aging agent for 100 parts of the emulsion polymerization solution obtained by polymerization 0 .03 parts were mixed to obtain a mixed solution. Then, the obtained mixed liquid was transferred to a coagulation tank, 30 parts of industrial water was added to 100 parts of this mixed liquid, the temperature was raised to 85 ° C., and then the obtained heavy liquid was stirred while stirring the mixed liquid. By adding 22 parts of magnesium sulfate to 100 parts of the polymer (polymer contained in the emulsion polymerization liquid), the polymer was coagulated, thereby obtaining a water-containing crumb of acrylic rubber (A1).
  • an aqueous sulfuric acid solution obtained by mixing 388 parts of industrial water and 0.13 part of concentrated sulfuric acid is added to 100 parts of the solid content of the hydrated crumb which has been washed with water as described above. After stirring for 5 minutes, the water-containing crumb was pickled by draining water from the coagulation tank. Next, 388 parts of pure water is added to 100 parts of solid content of the water-containing crumb subjected to pickling, and after stirring for 5 minutes at room temperature in the coagulation tank, the water is discharged from the coagulation tank, so that the water-containing crumb is discharged.
  • the hydrated crumb that had been washed with pure water was dried at 110 ° C. for 1 hour with a hot air dryer (belt conveyor type band dryer) to obtain a solid acrylic rubber (A1). . At this time, adhesion of acrylic rubber to the hot air dryer was not observed.
  • the resulting acrylic rubber (A1) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and its composition is 40.9 wt% ethyl acrylate unit, 35.0 wt% n-butyl acrylate unit, acrylic acid
  • the methoxyethyl unit was 20.0% by weight
  • the acrylonitrile unit was 1.5% by weight
  • the monochlorovinyl acetate unit was 2.6% by weight.
  • Example 2 An acrylic rubber (A2) was obtained in the same manner as in Example 1 except that 100 parts of sodium sulfate was used instead of 22 parts of magnesium sulfate as a coagulant.
  • the resulting acrylic rubber (A2) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and its composition is 40.9 wt% ethyl acrylate unit, 35.0 wt% n-butyl acrylate unit, acrylic acid
  • the methoxyethyl unit was 20.0% by weight
  • the acrylonitrile unit was 1.5% by weight
  • the monochlorovinyl acetate unit was 2.6% by weight.
  • Example 3 Monomer composition and polymerization step are the same as in Example 1, and an emulsion polymerization solution is obtained.
  • Mono (or di or tri) ( ⁇ -) as an anti-aging agent is obtained with respect to 100 parts of the emulsion polymerization solution obtained by polymerization.
  • a mixed solution was obtained by mixing 0.06 part of methylbenzyl) phenol (trade name “Raditex SP-50E”, manufactured by Higashi Chemical Co., Ltd., 50 wt% aqueous dispersion).
  • the resulting acrylic rubber (A3) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and the composition thereof is 40.9% by weight of ethyl acrylate units, 35.0% by weight of n-butyl acrylate units, acrylic acid
  • the methoxyethyl unit was 20.0% by weight
  • the acrylonitrile unit was 1.5% by weight
  • the monochlorovinyl acetate unit was 2.6% by weight.
  • an acrylic rubber composition was obtained in the same manner as in Example 1, and Mooney scorch test, measurement of hardness, tensile strength and elongation at break, air heat aging test, compression set test The results are shown in Table 1.
  • Example 4 An acrylic rubber (A4) was obtained in the same manner as in Example 1 except that instead of 22 parts of magnesium sulfate as a coagulant, 500 parts of a 20 wt% aqueous sodium sulfate solution (100 parts in terms of sodium sulfate) was used. .
  • the resulting acrylic rubber (A4) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
  • the acrylic rubber (A4) has a composition of 40.9% by weight of ethyl acrylate units and 35.0% of n-butyl acrylate units. % By weight, methoxyethyl acrylate unit 20.0% by weight, acrylonitrile unit 1.5% by weight, and monochlorovinyl acetate unit 2.6% by weight.
  • an acrylic rubber composition was obtained in the same manner as in Example 1, and Mooney scorch test, measurement of hardness, tensile strength and elongation at break, air heat aging test, compression set test The results are shown in Table 1.
  • Example 5 instead of sodium lauryl sulfate as an anionic emulsifier, sodium salt of polyoxyethylene alkylphenyl ether phosphate polyoxyethylene alkylphenol phosphate (trade name “phosphanol LO-529”, manufactured by Toho Chemical Co., Ltd., hydrophobic group A solid acrylic rubber (A5) was obtained in the same manner as in Example 1 except that a higher alcohol phosphate ester salt having 15 carbon atoms was used.
  • the resulting acrylic rubber (A5) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
  • the acrylic rubber (A5) had a composition of 40.9% by weight of ethyl acrylate units and 35.0% of n-butyl acrylate units. % By weight, methoxyethyl acrylate unit 20.0% by weight, acrylonitrile unit 1.5% by weight, and monochlorovinyl acetate unit 2.6% by weight.
  • an acrylic rubber composition was obtained in the same manner as in Example 1, and Mooney scorch test, measurement of hardness, tensile strength and elongation at break, air heat aging test, compression set test The results are shown in Table 1.
  • Example 6 instead of sodium lauryl sulfate as the anionic emulsifier, polyoxyethylene alkyl ether phosphate ester (trade name “phosphanol RA-600”, manufactured by Toho Chemical Co., Ltd., having 6 to 10 carbon atoms in the hydrophobic group (alkyl group)
  • a solid acrylic rubber (A6) was obtained in the same manner as in Example 1 except that a sodium salt of a higher alcohol phosphate ester salt was used.
  • the resulting acrylic rubber (A6) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
  • the acrylic rubber (A6) has a composition of 40.9% by weight of ethyl acrylate units and 35.0% of n-butyl acrylate units. % By weight, methoxyethyl acrylate unit 20.0% by weight, acrylonitrile unit 1.5% by weight, and monochlorovinyl acetate unit 2.6% by weight.
  • an acrylic rubber composition was obtained in the same manner as in Example 1, and Mooney scorch test, measurement of hardness, tensile strength and elongation at break, air heat aging test, compression set test The results are shown in Table 1.
  • Example 1 A solid acrylic rubber (C1) was obtained in the same manner as in Example 1 except that 4 parts of calcium chloride was used instead of 22 parts of magnesium sulfate as a coagulant.
  • the resulting acrylic rubber (C1) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and its composition is 40.9% by weight of ethyl acrylate units, 35.0% by weight of n-butyl acrylate units, acrylic acid The methoxyethyl unit was 20.0% by weight, the acrylonitrile unit was 1.5% by weight, and the monochlorovinyl acetate unit was 2.6% by weight.
  • an acrylic rubber composition was obtained in the same manner as in Example 1, and Mooney scorch test, measurement of hardness, tensile strength and elongation at break, air heat aging test, compression set test The results are shown in Table 1.
  • Example 2 A solid acrylic rubber (C2) was obtained in the same manner as in Example 1 except that 80 parts of sodium chloride was used instead of 22 parts of magnesium sulfate as a coagulant.
  • the resulting acrylic rubber (C2) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and its composition is 40.9% by weight of ethyl acrylate units, 35.0% by weight of n-butyl acrylate units, acrylic acid
  • the methoxyethyl unit was 20.0% by weight
  • the acrylonitrile unit was 1.5% by weight
  • the monochlorovinyl acetate unit was 2.6% by weight.
  • an acrylic rubber composition was obtained in the same manner as in Example 1, and Mooney scorch test, measurement of hardness, tensile strength and elongation at break, air heat aging test, compression set test The results are shown in Table 1.
  • a crosslinkable acrylic rubber produced by polymerizing a monomer containing a crosslinkable monomer using a redox catalyst in the presence of a nonionic emulsifier and an anionic emulsifier and coagulating with a metal sulfate (implemented) Examples 1 to 6) are completely inferior to those obtained by coagulation with conventionally used coagulants (Comparative Examples 1 and 2) in the normal state physical property test, the air heat aging test and the compression set test of the crosslinked product. You can see that there is no.
  • the acrylic rubber produced by the present invention has an initial physical property (Vmin: a smaller one is better), which can suppress nearly 10% compared to the prior art, and a long-term physical property (t5, t35: Both are better), but it is improved by nearly 10 to 50% compared to the prior art, and it can be seen that the storage stability is remarkably improved.
  • Vmin initial physical property
  • t5, t35 long-term physical property
  • the acrylic rubbers produced in the present invention show the same results as described above, and that the Vmin change is greatly improved. Recognize.
  • those using divalent metal sulfate Examples 1 and 3 can obtain a higher effect than those using monovalent metal sulfate. Recognize.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un procédé de production d'un caoutchouc acrylique, qui comprend : une étape de polymérisation en émulsion dans laquelle des monomères comprenant un ester (meth)acrylique comme ingrédient principal sont polymérisés en émulsion en présence à la fois d'un émulsifiant non ionique et d'un émulsifiant anionique à l'aide d'un initiateur de polymérisation pour obtenir une émulsion polymère; une étape de coagulation dans laquelle l'émulsion polymère est mise en contact avec un sulfate métallique pour coaguler l'émulsion et produire des granules hydratés; une étape de lavage dans laquelle les granules hydratés sont lavés; et une étape de séchage dans laquelle les granules hydratés lavés sont séchés.
PCT/JP2019/018096 2018-04-27 2019-04-26 Procédé de production de caoutchouc acrylique, et caoutchouc acrylique obtenu par ce procédé Ceased WO2019208821A1 (fr)

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SG11202010603TA SG11202010603TA (en) 2018-04-27 2019-04-26 Method for producing acrylic rubber, and acrylic rubber obtained by said production method
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