WO2016190214A1 - ニトリル基含有高飽和共重合体ゴム - Google Patents
ニトリル基含有高飽和共重合体ゴム Download PDFInfo
- Publication number
- WO2016190214A1 WO2016190214A1 PCT/JP2016/064876 JP2016064876W WO2016190214A1 WO 2016190214 A1 WO2016190214 A1 WO 2016190214A1 JP 2016064876 W JP2016064876 W JP 2016064876W WO 2016190214 A1 WO2016190214 A1 WO 2016190214A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer unit
- highly saturated
- saturated copolymer
- rubber
- nitrile group
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
-
- 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
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Definitions
- the present invention relates to a nitrile group-containing highly saturated copolymer rubber, and more specifically, a nitrile group-containing highly saturated copolymer rubber capable of providing a rubber cross-linked product excellent in swelling resistance in oil and curability in oil resistance. About.
- Nitrile group-containing highly saturated copolymer rubbers typified by hydrogenated acrylonitrile-butadiene copolymer rubbers, such as acrylonitrile-butadiene copolymer rubbers, have many carbon-carbon unsaturated bonds in the main chain structure. It is superior in heat resistance, oil resistance, ozone resistance, etc., compared to a nitrile group-containing copolymer rubber.
- Patent Document 1 includes an unsaturated nitrile monomer unit, a butadiene monomer unit, and an isoprene monomer unit.
- Nitrile group-containing highly saturated copolymer rubbers having a molar ratio with monomer units of 3: 1 or less have been proposed.
- the compression set resistance and the flexibility are improved at low temperatures. . It is also suitable for oil resistance and curability.
- the rubber cross-linked product obtained by using the nitrile group-containing highly saturated copolymer rubber described in Patent Document 1 has a fundamentally low resistance to swelling in oil and is not practically sufficient.
- the present invention has been made in view of such a situation, and is resistant to swelling in oil (small volume change in oil) and hardened in oil (hardness in oil containing a condensed aromatic compound).
- the present invention relates to a nitrile group-containing highly saturated copolymer rubber capable of providing an excellent rubber cross-linked product.
- the inventors of the present invention contain at least 28% by weight of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units and 20 to 72% by weight of conjugated diene monomer units.
- the nitrile group-containing highly saturated copolymer rubber having an iodine value of 120 or less has found that the above object can be achieved by setting the proportion of the isoprene unit in the conjugated diene monomer unit to 33% by weight or more.
- the present invention has been completed.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) is 28% by weight or more and the conjugated diene monomer unit (b) is 20 to 72% by weight
- a nitrile group-containing highly saturated copolymer rubber having a proportion of isoprene units of 33% by weight or more is provided.
- the nitrile group-containing highly saturated copolymer rubber of the present invention preferably contains an isoprene unit and a 1,3-butadiene unit as the conjugated diene monomer unit (b).
- the nitrile group-containing highly saturated copolymer rubber of the present invention preferably further contains an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c).
- the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c) has a (meth) acryl having an alkyl group having 1 to 18 carbon atoms. An acid ester is preferred.
- the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c) has an alkoxyalkyl group having 2 to 18 carbon atoms (meth). An acrylic ester is preferred.
- the nitrile group-containing highly saturated copolymer rubber of the present invention preferably further contains a carboxyl group-containing monomer unit (d).
- the carboxyl group-containing monomer unit (d) is preferably an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit.
- the crosslinkable rubber composition formed by containing said nitrile group containing highly saturated copolymer rubber and a crosslinking agent is provided. Furthermore, according to this invention, the rubber crosslinked material formed by bridge
- Nitrile group-containing highly saturated copolymer rubber capable of imparting water, and rubber crosslinking obtained by using such a nitrile group-containing highly saturated copolymer rubber and excellent in swelling resistance in oil and curability in oil resistance Things can be provided.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) is any ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
- the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) is 28% by weight or more in the total monomer units, It is preferably 28 to 50% by weight, more preferably 28 to 45% by weight, still more preferably 28 to 35% by weight, and particularly preferably 28 to 33% by weight.
- the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) is too small, the swelling property in oil resistance of the obtained rubber crosslinked product is lowered. On the other hand, if the amount is too large, the cold resistance of the resulting rubber cross-linked product is lowered.
- conjugated diene monomer that forms the conjugated diene monomer unit (b) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like.
- the content ratio of the conjugated diene monomer unit (b) in the nitrile group-containing highly saturated copolymer rubber of the present invention is 20 to 72% by weight, preferably 25 to 72% by weight, based on all monomer units. %, More preferably 30 to 72% by weight. If the content of the conjugated diene monomer unit (b) is too small, the resulting rubber cross-linked product will be inferior in rubber elasticity. On the other hand, if it is too high, the resulting rubber cross-linked product will have heat resistance and chemical resistance. Stability will be impaired.
- the conjugated diene monomer unit (b) is at least partially contained in the nitrile group-containing highly saturated copolymer rubber of the present invention in a hydrogenated state, and the above content ratio is hydrogenated. It is the ratio including the conjugated diene monomer unit (b) contained in a state.
- the nitrile group-containing highly saturated copolymer rubber of the present invention contains at least an isoprene unit as the conjugated diene monomer unit (b), and in the conjugated diene monomer unit (b),
- the content ratio of isoprene units is 33% by weight or more, preferably 33% by weight or more and 75% by weight or less, more preferably 33% by weight or more and 50% by weight or less.
- at least a part of the isoprene unit is contained in a hydrogenated state. Therefore, the above content ratio is contained in a hydrogenated state. It is also a ratio including isoprene units.
- the obtained rubber cross-linked product can be condensed while improving the swelling resistance in oil. It can have a small change in hardness in oil containing an aromatic compound, that is, it can have excellent curability in oil resistance.
- the content ratio of the isoprene unit is too small, the resulting rubber cross-linked product is inferior in resistance to oil-curing and has a large change in hardness in the oil containing the condensed aromatic compound.
- the nitrile group-containing highly saturated copolymer rubber of the present invention may be any conjugated diene monomer unit (b) as long as it contains an isoprene unit in the above range.
- the conjugated diene monomer unit (b) may contain only an isoprene unit, and may contain an isoprene unit and a unit which consists of 1 type, or 2 or more types of conjugated diene monomers other than an isoprene unit.
- the obtained rubber cross-linked product can have an excellent balance between curability in oil resistance and cold resistance, so that the conjugated diene monomer unit (b) is an isoprene unit and one other than the isoprene unit. It preferably contains a unit composed of two or more conjugated diene monomers, and more preferably contains an isoprene unit and a 1,3-butadiene unit.
- the content ratio of the unit consisting of is preferably 0% by weight or more, more preferably 25% by weight or more, and further preferably 50% by weight or more. That is, the upper limit of the content ratio of the isoprene unit in the conjugated diene monomer unit (b) is preferably 100% by weight or less, more preferably 75% by weight or less, and further preferably 50% by weight or less.
- the nitrile group-containing highly saturated copolymer rubber of the present invention includes an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) and a conjugated diene monomer unit (b).
- -It may contain an ethylenically unsaturated monocarboxylic acid ester monomer unit (c).
- the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c) forming the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit includes methyl acrylate, ethyl acrylate, acrylic acid (Meth) acrylic acid esters having an alkyl group having 1 to 18 carbon atoms such as n-butyl, isobutyl acrylate, n-dodecyl acrylate, methyl methacrylate, and ethyl methacrylate (“methacrylic acid esters and acrylic acid esters”) Abbreviations, the same shall apply hereinafter.); Carbon number such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxypropyl acrylate, methoxybutyl acrylate, ethoxydodecyl acrylate, methoxyethyl methacrylate, methoxybutyl methacryl
- (meth) acrylic having an alkyl group having 1 to 18 carbon atoms from the viewpoint of improving the cold resistance of the rubber cross-linked product in addition to further improving the swelling resistance of the resulting rubber cross-linked product in oil.
- Acid esters and (meth) acrylic acid esters having an alkoxyalkyl group having 2 to 18 carbon atoms are preferred, and n-butyl acrylate and methoxyethyl acrylate are particularly preferred.
- a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms is preferable from the viewpoint of particularly improving cold resistance, and from the viewpoint of improving the swelling resistance in oil, 2 to 18 carbon atoms.
- the (meth) acrylic acid ester having an alkoxyalkyl group is preferred.
- the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer may be used alone or in combination of two or more.
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid in nitrile group-containing highly saturated copolymer rubber of the present invention in the case of containing ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c)
- the content of the ester monomer unit (c) is preferably 10 to 52% by weight, more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight in the total monomer units.
- the nitrile group-containing highly saturated copolymer rubber of the present invention is used as necessary, ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a), conjugated diene monomer unit (b), and as required.
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c) it may contain a carboxyl group-containing monomer unit (d).
- the carboxyl group-containing monomer that forms the carboxyl group-containing monomer unit (d) can be copolymerized with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer and is not esterified.
- the monomer is not particularly limited as long as it is a monomer having one or more substituted (free) carboxyl groups.
- a carboxyl group can be introduced into the nitrile group-containing highly saturated copolymer rubber of the present invention.
- Examples of the carboxyl group-containing monomer used in the present invention include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomers, ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acid monomers, and ⁇ , ⁇ -Ethylenically unsaturated dicarboxylic acid monoester monomers and the like.
- the carboxyl group-containing monomer also includes monomers in which the carboxyl group of these monomers forms a carboxylate.
- an anhydride of an ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid can also be used as a carboxyl group-containing monomer because it forms a carboxyl group by cleaving the acid anhydride group after copolymerization.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, and cinnamic acid.
- Examples of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid monomers include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allylmalonic acid, and teraconic acid.
- Examples of the anhydride of ⁇ , ⁇ -unsaturated polyvalent carboxylic acid include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
- maleic acid monoalkyl esters such as monomethyl maleate, monoethyl maleate, monopropyl maleate, mono n-butyl maleate; monocyclopentyl maleate, Maleic acid monocycloalkyl esters such as monocyclohexyl maleate and monocycloheptyl maleate; Monoalkyl cycloalkyl esters of maleic acid such as monomethylcyclopentyl maleate and monoethylcyclohexyl maleate; Monomethyl fumarate, monoethyl fumarate and monofumarate Fumaric acid monoalkyl esters such as propyl and mono-n-butyl fumarate; fumaric acid such as monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate Monocycloalkyl esters of fumaric acid such as monomethyl
- the carboxyl group-containing monomer may be used alone or in combination of two or more.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers are preferred, and ⁇ , ⁇ -ethylenic monomers are preferred because the effect of improving compression set resistance becomes more remarkable.
- Unsaturated dicarboxylic acid monoalkyl ester monomers are more preferred, maleic acid monoalkyl esters are more preferred, and mono-n-butyl maleate is particularly preferred.
- the content ratio of the carboxyl group-containing monomer unit (d) in the highly saturated copolymer rubber containing the nitrile group of the present invention is In the unit, it is preferably 0 to 10% by weight, more preferably 2 to 9% by weight, still more preferably 3 to 8% by weight.
- the nitrile group-containing highly saturated copolymer rubber of the present invention includes an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a), a conjugated diene monomer unit (b), and, if necessary,
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c) and carboxyl group-containing monomer unit (d) used other monomers copolymerizable with these monomers It may contain a monomer unit. Examples of such other monomers include ethylene, ⁇ -olefin monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and copolymerizable anti-aging agents.
- the ⁇ -olefin monomer preferably has 3 to 12 carbon atoms, and examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
- aromatic vinyl monomers examples include styrene, ⁇ -methylstyrene, vinyl pyridine and the like.
- fluorine-containing vinyl monomers examples include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
- copolymerizable anti-aging agents examples include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilino). Phenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
- the content of other copolymerizable monomer units is preferably 50% by weight or less, more preferably 40% by weight, based on all monomer units. % Or less, more preferably 10% by weight or less.
- the iodine value in the highly saturated copolymer rubber containing nitrile group of the present invention is 120 or less, preferably 80 or less, more preferably 60 or less, and particularly preferably 50 or less. If the iodine value is too high, the heat resistance and ozone resistance of the resulting rubber cross-linked product may be reduced.
- the polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) of the nitrile group-containing highly saturated copolymer rubber of the present invention is preferably 10 to 200, more preferably 15 to 150, still more preferably 15 to 100, and particularly preferably 30 to 90.
- the polymer Mooney viscosity is 10 or more, the mechanical properties of the obtained rubber cross-linked product are improved.
- the polymer Mooney viscosity is 200 or less, the processability is improved when a crosslinking agent is added to form a crosslinkable rubber composition.
- the method for producing the nitrile group-containing highly saturated copolymer rubber of the present invention is not particularly limited, but the above-mentioned monomers are copolymerized, and the carbon-carbon double bonds in the resulting copolymer are hydrogenated. Can be manufactured by.
- the polymerization method is not particularly limited and may be a known emulsion polymerization method or solution polymerization method. From the viewpoint of industrial productivity, the emulsion polymerization method is preferable. In emulsion polymerization, in addition to an emulsifier, a polymerization initiator, and a molecular weight modifier, a commonly used polymerization auxiliary material can be used.
- nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester; myristic acid, palmitic acid, oleic acid And salts of fatty acids such as linolenic acid, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, anionic emulsifiers such as higher alcohol sulfates and alkylsulfosuccinates; sulfoesters of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid sulfate esters, sulfoalkyl aryl ethers and other copolymerizable emulsifiers.
- the amount of the emulsifier added is preferably 0.1 to 10 parts
- the polymerization initiator is not particularly limited as long as it is a radical initiator, but inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene Hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3, 5, 5 Organic peroxides such as trimethylhexanoyl peroxide and t-butylperoxyisobutyrate; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc.
- inorganic peroxides
- polymerization initiators can be used alone or in combination of two or more.
- an inorganic or organic peroxide is preferable.
- a peroxide is used as the polymerization initiator, it can be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite or ferrous sulfate.
- the addition amount of the polymerization initiator is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
- the molecular weight modifier is not particularly limited, but mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, methylene bromide; ⁇ -methylstyrene dimer And sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide. These can be used alone or in combination of two or more.
- the amount of the molecular weight modifier used is preferably 0.1 to 0.8 parts by weight with respect to 100 parts by weight of the total monomers.
- water is used as a medium for emulsion polymerization.
- the amount of water is preferably 80 to 500 parts by weight, more preferably 80 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 stabilizer, a dispersant, a pH adjuster, an oxygen scavenger, and a particle size adjuster can be used as necessary. In using these, neither the kind nor the usage-amount is specifically limited.
- the obtained copolymer may be subjected to hydrogenation (hydrogenation reaction) of the copolymer as necessary. Hydrogenation may be carried out by a known method. After coagulating a latex of a copolymer obtained by emulsion polymerization, an oil layer hydrogenation method in which hydrogenation is performed in an oil layer, or a latex of the obtained copolymer is hydrogenated as it is. And water layer hydrogenation method.
- the copolymer latex prepared by emulsion polymerization is preferably dissolved in an organic solvent through salting out, coagulation with alcohol, filtration and drying.
- a hydrogenation reaction oil layer hydrogenation method
- the resulting hydride is poured into a large amount of water, solidified, filtered and dried to obtain the nitrile group-containing highly saturated copolymer rubber of the present invention. Can do.
- a known coagulant such as sodium chloride, calcium chloride, or aluminum sulfate can be used for coagulation of latex by salting out. Moreover, it may replace with solidification by salting out and may perform coagulation using alcohol, such as methanol.
- the solvent for the oil layer hydrogenation method is not particularly limited as long as it is a liquid organic compound that dissolves the copolymer obtained by emulsion polymerization, but benzene, chlorobenzene, toluene, xylene, hexane, cyclohexane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate. Cyclohexanone and acetone are preferably used.
- any known selective hydrogenation catalyst can be used without limitation.
- Palladium-based catalysts and rhodium-based catalysts are preferable, and palladium-based catalysts (such as palladium acetate, palladium chloride and palladium hydroxide) are preferred. More preferred. Two or more of these may be used in combination. In this case, it is preferable to use a palladium-based catalyst as the main active ingredient.
- These catalysts are usually used by being supported on a carrier.
- the carrier include silica, silica-alumina, alumina, diatomaceous earth, activated carbon and the like.
- the amount of catalyst used is preferably 10 to 20000 ppm by weight, more preferably 100 to 15000 ppm by weight, based on the copolymer.
- the latex of the copolymer prepared by emulsion polymerization is diluted with water as necessary to carry out the hydrogenation reaction.
- the water layer hydrogenation method is a water layer direct hydrogenation method in which hydrogen is supplied to a reaction system in the presence of a hydrogenation catalyst to perform hydrogenation, and reduction and hydrogenation are performed in the presence of an oxidizing agent, a reducing agent and an activator.
- An aqueous layer indirect hydrogenation method can be mentioned, and among these, the aqueous layer direct hydrogenation method is preferable.
- the copolymer concentration (concentration in the latex state) in the aqueous layer is preferably 40% by weight or less in order to prevent aggregation.
- a hydrogenation catalyst will not be specifically limited if it is a compound which is hard to decompose
- the palladium catalyst include palladium salts of carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid, and phthalic acid; palladium chloride, dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) palladium, Palladium chloride such as ammonium hexachloropalladium (IV); Iodide such as palladium iodide; Palladium sulfate dihydrate and the like.
- palladium salts of carboxylic acids, dichloro (norbornadiene) palladium and ammonium hexachloropalladium (IV) are particularly preferred.
- the amount of the hydrogenation catalyst used may be appropriately determined, but is preferably 5 to 20000 ppm by weight, more preferably 10 to 15000 ppm by weight, based on the copolymer obtained by polymerization.
- the hydrogenation catalyst in the latex is removed after completion of the hydrogenation reaction.
- an adsorbent such as activated carbon or ion exchange resin is added to adsorb the hydrogenation catalyst with stirring, and then the latex is filtered or centrifuged. It is also possible to leave it in the latex without removing the hydrogenation catalyst.
- the latex after the hydrogenation reaction thus obtained is subjected to coagulation by salting out, filtration, drying, and the like, whereby the nitrile group-containing highly saturated copolymer of the present invention is obtained.
- a polymer rubber can be obtained.
- the filtration and drying steps subsequent to coagulation can be performed by known methods.
- the crosslinkable rubber composition of the present invention comprises the nitrile group-containing highly saturated copolymer rubber of the present invention and a crosslinking agent.
- the crosslinkable rubber composition of the present invention may contain two or more nitrile group-containing highly saturated copolymer rubbers as the nitrile group-containing highly saturated copolymer rubber of the present invention.
- Different types of monomer units constituting the nitrile group-containing highly saturated copolymer rubber and those having different content ratios can be used in appropriate combination.
- the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit (c) has 1 to 18 carbon atoms.
- a combination containing a (meth) acrylic acid ester having an alkyl group and a (meth) acrylic acid ester having a C 2-18 alkoxyalkyl group can be used in combination.
- the crosslinking agent is not particularly limited as long as it can crosslink the nitrile group-containing highly saturated copolymer rubber of the present invention, and examples thereof include a sulfur crosslinking agent, an organic peroxide crosslinking agent, and a polyamine crosslinking agent. .
- Sulfur-based cross-linking agents include powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, and the like; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, N, Sulfur-containing compounds such as N′-dithio-bis (hexahydro-2H-azepin-2-one), phosphorus-containing polysulfides, polymer polysulfides; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4′-morpholino And sulfur donating compounds such as dithio) benzothiazole. These can be used individually by 1 type or in combination of multiple types.
- organic peroxide crosslinking agents include dicumyl peroxide, cumene hydroperoxide, t-butylcumyl peroxide, paramentane hydroperoxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,4-bis (t-butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-3,3-trimethylcyclohexane, 4,4-bis- (t-butyl-peroxy) -n-butylvale 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, 1,1-di-t-butyl Peroxy-3,5,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, t-butyl
- the polyamine-based crosslinking agent is not particularly limited as long as it is a compound having two or more amino groups or a compound having two or more amino groups at the time of crosslinking.
- a compound in which a plurality of hydrogen atoms of a group hydrocarbon are substituted with an amino group or a hydrazide structure (a structure represented by —CONHNH 2 , CO represents a carbonyl group), and a compound that is in the form of the compound upon crosslinking are preferred .
- polyamine-based cross-linking agent examples include aliphatic polyvalent compounds such as hexamethylene diamine, hexamethylene diamine carbamate, N, N-dicinnamylidene-1,6-hexane diamine, tetramethylene pentamine, and hexamethylene diamine cinnamaldehyde adduct.
- aliphatic polyvalent amines and aromatic polyvalent amines are preferable from the viewpoint that the effects of the present invention can be made more remarkable, and hexamethylenediamine carbamate and 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane is more preferred, and hexamethylenediamine carbamate is particularly preferred.
- the content of the crosslinking agent in the crosslinkable rubber composition of the present invention is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the nitrile group-containing highly saturated copolymer rubber. 1 to 15 parts by weight.
- crosslinking agent when a polyamine-based crosslinking agent is used as the crosslinking agent, it is preferable to further contain a basic crosslinking accelerator.
- basic crosslinking accelerators include compounds represented by the following general formula (1), basic crosslinking accelerators having a cyclic amidine structure, guanidine basic crosslinking accelerators, and aldehyde amine basic crosslinking accelerators. Agents and the like.
- R 1 and R 2 may each independently have an alkyl group having 1 to 12 carbon atoms which may have a substituent, or may have a substituent.
- It is a cycloalkyl group having 5 to 12 carbon atoms.
- R 1 and R 2 are each an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted cycloalkyl group having 5 to 12 carbon atoms.
- a cycloalkyl group having 5 to 12 carbon atoms which may have a group is preferable, and a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent is particularly preferable.
- R 1 and R 2 are preferably not substituted.
- R 1 and R 2 have a substituent include a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, and a halogen atom.
- a compound represented by the following general formula (2) is more preferable from the viewpoint that processability and scorch stability can be further improved.
- R 3 and R 4 are each independently a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent.
- R 3 and R 4 are cycloalkyl groups having 5 to 8 carbon atoms which may have a substituent, but may be cycloalkyl groups which may have a substituent having 5 or 6 carbon atoms. Is preferable, and a cycloalkyl group which may have a substituent having 6 carbon atoms is more preferable. R 3 and R 4 preferably have no substituent.
- R 3 and R 4 have a substituent include a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, and a halogen atom.
- Specific examples of the compound represented by the general formula (1) include dicycloalkylamines such as dicyclopentylamine, dicyclohexylamine and dicycloheptylamine; N-methylcyclopentylamine, N-butylcyclopentylamine and N-heptyl.
- Examples of the basic crosslinking accelerator having a cyclic amidine structure include 1,8-diazabicyclo [5,4,0] undecene-7 (hereinafter sometimes abbreviated as “DBU”) and 1,5-diazabicyclo [4, 3,0] nonene-5 (hereinafter sometimes abbreviated as “DBN”), 1-methylimidazole, 1-ethylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1,2-dimethylimidazole, 1-ethyl- 2-methylimidazole, 1-methoxyethylimidazole, 1-phenyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-methyl-2-phenylimidazole, 1-methyl-2-benzylimidazole, 1,4 -Dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole 1,4-dimethyl-2-ethylimidazole, 1-methyl
- 1,8-diazabicyclo [5,4,0] undecene-7 and 1,5-diazabicyclo [4,3,0] nonene-5 are preferable.
- 8-diazabicyclo [5,4,0] undecene-7 is more preferred.
- the guanidine-based basic crosslinking accelerator include tetramethylguanidine, tetraethylguanidine, diphenylguanidine, 1,3-di-ortho-tolylguanidine, orthotolyl biguanide and the like.
- aldehyde amine basic crosslinking accelerator include n-butyraldehyde aniline and acetaldehyde ammonia.
- guanidine basic crosslinking accelerators compounds represented by the above general formula (1), guanidine basic crosslinking accelerators, and basic crosslinking accelerators having a cyclic amidine structure are preferable.
- a compound represented by the formula and a basic crosslinking accelerator having a cyclic amidine structure are more preferred.
- the compound represented by the general formula (1) may be a mixture of an alkylene glycol or an alcohol such as an alkyl alcohol having 5 to 20 carbon atoms, and an inorganic acid and / or an organic acid. May be included. Further, as the compound represented by the general formula (1), a salt is formed by the compound represented by the general formula (1) and the inorganic acid and / or organic acid, and a complex is formed with alkylene glycol. It may be.
- the basic crosslinking accelerator having a cyclic amidine structure may form a salt with an organic carboxylic acid or an alkyl phosphoric acid.
- the blending amount in the crosslinkable rubber composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the nitrile group-containing highly saturated copolymer rubber. More preferably 0.2 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight.
- the crosslinkable nitrile rubber composition of the present invention includes a compounding agent usually used in the rubber field, for example, a reinforcing agent such as carbon black or silica, a filler such as calcium carbonate, talc or clay, Metal oxides such as zinc oxide and magnesium oxide, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid metal salts such as zinc methacrylate and zinc acrylate, co-crosslinking agent, crosslinking aid, crosslinking retarder, anti-aging agent, oxidation Anti-scorching agent such as inhibitor, light stabilizer, primary amine, activator such as diethylene glycol, coupling agent, plasticizer, processing aid, lubricant, adhesive, lubricant, flame retardant, antifungal agent, acid acceptor Further, an antistatic agent, a pigment, a foaming agent and the like can be blended.
- a compounding agent usually used in the rubber field for example, a reinforcing agent such as carbon black or silica, a filler
- the coupling agent examples include silane coupling agents, aluminum coupling agents, titanate coupling agents, and the like.
- the silane coupling agent is not particularly limited, and specific examples thereof include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptomethyltrimethoxylane, ⁇ -mercaptomethyltriethoxylane, ⁇ -mercaptohexamethyldisilazane, bis Silane coupling agents containing sulfur such as (3-triethoxysilylpropyl) tetrasulfane and bis (3-triethoxysilylpropyldisulfane); ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyl Epoxy group-containing silane coupling agents such as methyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane,
- the aluminum coupling agent is not particularly limited, and specific examples thereof include acetoalkoxyaluminum diisopropylate.
- the titanate coupling agent is not particularly limited, and specific examples thereof include isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, tetraisopropyl Bis (dioctyl phosphite
- carbon black examples include furnace black, acetylene black, thermal black, channel black, Austin black, and graphite. These can be used alone or in combination.
- silica examples include natural silica such as quartz powder and silica powder; synthetic silica such as silicic anhydride (silica gel, aerosil, etc.) and hydrous silicic acid; among these, synthetic silica is preferable.
- These silicas may be surface-treated with a coupling agent or the like.
- the coupling agent used for the surface treatment for example, those described above can be used.
- the co-crosslinking agent is not particularly limited, but is preferably a low molecular or high molecular compound having a plurality of radical-reactive unsaturated groups in the molecule.
- a polyfunctional vinyl compound such as divinylbenzene or divinylnaphthalene; Isocyanurates such as allyl isocyanurate and trimethallyl isocyanurate; cyanurates such as triallyl cyanurate; maleimides such as N, N′-m-phenylene dimaleimide; diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl Allyl esters of polyvalent acids such as fumarate, diallyl sebacate, triallyl phosphate; diethylene glycol bisallyl carbonate; ethylene glycol diallyl ether, triallyl ether of trimethylolpropane, pentae Allyl ethers such as partial allyl ethers of putt; allyl-modified resins such
- the plasticizer is not particularly limited, but trimellitic acid plasticizer, pyromellitic acid plasticizer, ether ester plasticizer, polyester plasticizer, phthalic acid plasticizer, adipate ester plasticizer, phosphoric acid
- trimellitic acid plasticizer pyromellitic acid plasticizer
- ether ester plasticizer polyester plasticizer
- phthalic acid plasticizer adipate ester plasticizer
- phosphoric acid An ester plasticizer, a sebacic acid ester plasticizer, an alkyl sulfonic acid ester compound plasticizer, an epoxidized vegetable oil plasticizer, or the like can be used.
- trimellitic acid tri-2-ethylhexyl trimellitic acid isononyl ester, trimellitic acid mixed linear alkyl ester, dipentaerythritol ester, pyromellitic acid 2-ethylhexyl ester, polyether ester (molecular weight 300 to About 5000), bis [2- (2-butoxyethoxy) ethyl adipate], dioctyl adipate, polyester based on adipic acid (molecular weight about 300-5000), dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, phosphoric acid
- examples include tricresyl, dibutyl sebacate, alkylsulfonic acid phenyl ester, epoxidized soybean oil, diheptanoate, di-2-ethylhexanoate, and didecanoate. These can be used alone or in combination.
- examples of such rubbers include acrylic rubber, ethylene-acrylic acid copolymer rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, Examples include epichlorohydrin rubber, fluorine rubber, urethane rubber, chloroprene rubber, silicone rubber, natural rubber, and polyisoprene rubber.
- the blending amount in the crosslinkable rubber composition is based on 100 parts by weight of the nitrile group-containing highly saturated copolymer rubber of the present invention.
- the amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still more preferably 10 parts by weight or less.
- the crosslinkable rubber composition of the present invention is prepared by mixing each of the above components preferably in a non-aqueous system.
- the method for preparing the crosslinkable rubber composition of the present invention is not limited, but usually the components excluding the crosslinker and heat-labile components are primarily kneaded with a mixer such as a Banbury mixer, an intermixer, or a kneader. Then, it can transfer to an open roll etc., and can prepare by adding a crosslinking agent and a heat unstable component, and carrying out secondary kneading
- the primary kneading is usually performed at a temperature of 10 to 200 ° C., preferably 30 to 180 ° C.
- the reaction is performed at a temperature of 20 to 60 ° C. for 1 minute to 1 hour, preferably 1 minute to 30 minutes.
- Cross-linked rubber The cross-linked rubber of the present invention is obtained by cross-linking the cross-linkable rubber composition of the present invention described above.
- the rubber cross-linked product of the present invention is formed by using the cross-linkable 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, a roll, etc., and heated. Can be produced by carrying out a crosslinking reaction and fixing the shape as a crosslinked product.
- 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 120 ° C.
- the crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C.
- the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 1 hour.
- secondary cross-linking may be performed by heating.
- a heating method a general 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 thus obtained is obtained by using the nitrile group-containing highly saturated copolymer rubber of the present invention described above, and is resistant to swelling in oil (the volume change in oil is small). ), And curability in oil resistance (small change in hardness in oil containing condensed aromatic compound). For this reason, the rubber cross-linked product of the present invention makes use of such characteristics, and O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, well head seals, shock absorber seals, pneumatic equipment seals, air conditioners.
- Various seal materials such as seals, seals for rolling devices (rolling bearings, automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.), valves and valve seats, BOPs (Blow Out Preventer), platters; Intake manifold and series Intake manifold gasket attached to the connecting part of the cylinder head, cylinder head gasket attached to the connecting part of the cylinder block and the cylinder head, rocker cover gasket attached to the connecting part of the rocker cover and the cylinder head, oil pan, Oil pan gasket attached to the connecting part to the cylinder block or transmission case, gasket for fuel cell separator attached between a pair of housings sandwiching a unit cell having a positive electrode, an electrolyte plate and a negative electrode, for a top cover of a hard disk drive
- gaskets such as
- the iodine value of the highly saturated copolymer rubber containing the iodine value nitrile group was measured according to JIS K 6235.
- composition of nitrile group-containing highly saturated copolymer rubber The content ratio of each monomer unit constituting the nitrile group-containing highly saturated copolymer rubber was measured by the following method. That is, the content ratio of the mono-n-butyl maleate unit was determined by determining the number of moles of carboxyl groups with respect to 100 g of the nitrile group-containing highly saturated copolymer rubber after hydrogenation, by the method for measuring “carboxyl group content”. The number of moles calculated was converted to the amount of mono n-butyl maleate units. The content ratio of 1,3-butadiene units (including hydrogenated portions) and isoprene units (including hydrogenated portions) was measured by the following method.
- the content ratio of the acrylonitrile unit was calculated by measuring the nitrogen content in the highly saturated copolymer rubber containing nitrile group after hydrogenation by Kjeldahl method according to JIS K6384. The content ratio of methoxyethyl acrylate units and n-butyl acrylate units was calculated as the balance of each monomer unit.
- a swelling resistance test in oil resistance was performed.
- IRDH method international rubber hardness tester
- TR test Cold resistance test
- a sheet-like rubber cross-linked product was obtained, and the cold resistance of the rubber cross-linked product was measured by a TR test (low temperature elastic recovery test) in accordance with JIS K6261.
- TR test low temperature elastic recovery test
- the stretched rubber cross-linked product was frozen and the temperature was continuously raised to measure the recoverability of the stretched rubber cross-linked product.
- the temperature TR10 at the time of (recovery) was measured. It can be determined that the lower the TR10, the better the cold resistance.
- Production Example 1 (Production of nitrile group-containing highly saturated copolymer rubber (n1))
- n1 nitrile group-containing highly saturated copolymer rubber
- 180 parts of ion-exchanged water, 25 parts of a 10% aqueous sodium dodecylbenzenesulfonate solution, 43 parts of acrylonitrile, 4.5 parts of mono-n-butyl maleate, and t-dodecyl mercaptan (molecular weight regulator) 75 parts were charged in that order, and the internal gas was replaced with nitrogen three times.
- 34 parts of 1,3-butadiene and 18.5 parts of isoprene were charged.
- the reactor was kept at 10 ° C., 0.1 part of cumene hydroperoxide (polymerization initiator), a reducing agent, and an appropriate amount of chelating agent were charged, and the polymerization reaction was continued while stirring, so that the polymerization conversion rate was 80%. At that time, 0.1 part of a 10% by weight hydroquinone aqueous solution (polymerization terminator) was added to terminate the polymerization reaction. Subsequently, the residual monomer was removed at a water temperature of 60 ° C. to obtain a latex of nitrile group-containing copolymer rubber (X1) (solid content concentration: 25% by weight).
- X1 solid content concentration: 25% by weight
- the latex of nitrile rubber (X1) and the palladium catalyst are added to the autoclave so that the palladium content relative to the dry weight of the rubber contained in the latex of nitrile rubber (X1) obtained above is 5,000 ppm. (1% by weight palladium acetate / acetone solution mixed with equal weight of ion-exchanged water) was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a nitrile group-containing highly saturated copolymer rubber. A latex (n1) was obtained.
- the latex of the obtained nitrile group-containing highly saturated copolymer rubber (n1) was coagulated by adding twice the volume of methanol, and then vacuum-dried at 60 ° C. for 12 hours to obtain a nitrile group-containing highly saturated copolymer rubber ( n1) was obtained.
- the resulting nitrile group-containing highly saturated copolymer rubber (n1) had an iodine value of 28.
- the resulting nitrile group-containing highly saturated copolymer rubber (n1) comprises 44% by weight of acrylonitrile units, 28% by weight of isoprene units (including hydrogenated portions), and butadiene units (including hydrogenated portions). ) 23 wt%, mono n-butyl maleate unit 5 wt%.
- Production Examples 2 to 26 (Production of nitrile group-containing highly saturated copolymer rubber (n2) to (n26))
- a nitrile group-containing highly saturated copolymer rubber (n2) to (n26) is produced in the same manner as in Production Example 1 except that the type and amount of the monomer used for the polymerization are changed as shown in Tables 1 and 2.
- Tables 1 and 2 show the iodine values and monomer compositions of the resulting nitrile group-containing highly saturated copolymer rubbers (n2) to (n26).
- the polymerization conversion rate in the polymerization reaction and the amount of palladium catalyst in the hydrogenation reaction were changed to those shown in Tables 1 and 2.
- methoxyethyl acrylate or n-butyl acrylate is blended, methoxyethyl acrylate or n-butyl acrylate is added after acrylonitrile is added, and methoxyethyl acrylate or n-butyl acrylate is added. Mono n-butyl maleate was added in this order.
- Example 1 Using a Banbury mixer, 100 parts of the nitrile group-containing highly saturated copolymer rubber (n1) obtained in Production Example 1, 50 parts of FEF carbon (trade name “Seast SO”, manufactured by Tokai Carbon Co., Ltd., carbon black), Trimellitic acid tri-2-ethylhexyl (trade name "Adekasizer C-8", manufactured by ADEKA, plasticizer) 1 part, trimellitic acid isononyl ester (trade name "Adekasizer C-9N", manufactured by ADEKA) 1 part, 1 part of polyetherester plasticizer (trade name “Adekaizer RS-700”, manufactured by ADEKA) 1 part of polyetherester plasticizer (trade name “Adekaizer RS-735”, manufactured by ADEKA) , 1 part of adipic acid ether ester plasticizer (trade name “ADEKA SIZER RS-107”, manufactured by ADEKA), stearic acid Parts, polyoxyethylene alkyl ether phosphate ester (trade name “
- a rubber cross-linked product is obtained using the cross-linkable rubber composition prepared above, and the obtained rubber cross-linked product is subjected to a resistance test in oil resistance, a swelling test in oil resistance and a cold resistance test. Went. The results are shown in Table 1.
- Examples 2 to 9 Instead of the nitrile group-containing highly saturated copolymer rubber (n1) obtained in Production Example 1, the nitrile group-containing highly saturated copolymer rubber (n2) to (n9) obtained in Production Examples 2 to 9 was used. Except for the above, a crosslinkable rubber composition was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. The blending amount of hexamethylenediamine carbamate as the cross-linking agent was varied in proportion to the mono n-butyl maleate unit.
- Example 10 Using a Banbury mixer, 100 parts of the nitrile group-containing highly saturated copolymer rubber (n10) obtained in Production Example 10, 50 parts of FEF carbon (trade name “Seast SO”, manufactured by Tokai Carbon Co., Ltd., carbon black), Trimellitic acid tri-2-ethylhexyl (trade name "Adekasizer C-8", manufactured by ADEKA, plasticizer) 1 part, trimellitic acid isononyl ester (trade name "Adekasizer C-9N", manufactured by ADEKA) 1 part, 1 part of polyetherester plasticizer (trade name “Adekaizer RS-700”, manufactured by ADEKA) 1 part of polyetherester plasticizer (trade name “Adekaizer RS-735”, manufactured by ADEKA) , 1 part of adipic acid ether ester plasticizer (trade name “ADEKA SIZER RS-107”, manufactured by ADEKA), stearin (Crosslinking accelerating agent) 1 part, zinc oxide (2 types of zinc white,
- a rubber cross-linked product is obtained using the cross-linkable rubber composition prepared above, and the obtained rubber cross-linked product is subjected to a resistance test in oil resistance, a swelling test in oil resistance and a cold resistance test. Went. The results are shown in Table 1.
- Examples 11-18 Instead of the nitrile group-containing highly saturated copolymer rubber (n10) obtained in Production Example 10, the nitrile group-containing highly saturated copolymer rubber (n11) to (n18) obtained in Production Examples 11 to 18 was used. Except for the above, a crosslinkable rubber composition was obtained in the same manner as in Example 10 and evaluated in the same manner. The results are shown in Tables 1 and 2.
- Comparative Examples 1 to 3 Instead of the nitrile group-containing highly saturated copolymer rubber (n1) obtained in Production Example 1, the nitrile group-containing highly saturated copolymer rubber (n19) to (n21) obtained in Production Examples 19 to 21 was used. Except for the above, a crosslinkable rubber composition was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2. The blending amount of hexamethylenediamine carbamate as the cross-linking agent was varied in proportion to the mono n-butyl maleate unit.
- Comparative Examples 4-8 Instead of the nitrile group-containing highly saturated copolymer rubber (n10) obtained in Production Example 10, the nitrile group-containing highly saturated copolymer rubber (n22) to (n26) obtained in Production Examples 22 to 26 was used. Except for the above, a crosslinkable rubber composition was obtained in the same manner as in Example 10 and evaluated in the same manner. The results are shown in Table 2.
- the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) and the conjugated diene monomer unit (b), and the iodine value are within the predetermined range of the present invention,
- the rubber cross-linked product obtained by using the nitrile group-containing highly saturated copolymer rubber in which the proportion of the isoprene unit in the conjugated diene monomer unit (b) is 33% by weight or more has a volume in the oil.
- the change and the hardness change in the oil containing the condensed aromatic compound were both small, and the oil was excellent in swelling resistance in oil and curability in oil resistance (Examples 1 to 18).
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明のニトリル基含有高飽和共重合体ゴムは、α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)をさらに含有することが好ましい。
本発明のニトリル基含有高飽和共重合体ゴムにおいて、前記α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)が、炭素数1~18のアルキル基を有する(メタ)アクリル酸エステルであることが好ましい。
本発明のニトリル基含有高飽和共重合体ゴムにおいて、前記α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)が、炭素数2~18のアルコキシアルキル基を有する(メタ)アクリル酸エステルであることが好ましい。
本発明のニトリル基含有高飽和共重合体ゴムは、カルボキシル基含有単量体単位(d)をさらに含有することが好ましい。
本発明のニトリル基含有高飽和共重合体ゴムにおいて、前記カルボキシル基含有単量体単位(d)が、α,β-エチレン性不飽和ジカルボン酸モノエステル単量体単位であることが好ましい。
さらに、本発明によれば、上記の架橋性ゴム組成物を架橋してなるゴム架橋物が提供される。
α,β-エチレン性不飽和ニトリル単量体単位(a)28重量%以上、および共役ジエン単量体単位(b)20~72重量%を含有し、ヨウ素価が120以下であるニトリル基含有高飽和共重合体ゴムであって、前記共役ジエン単量体単位(b)は、少なくとも一部は水素化されており、前記共役ジエン単量体単位(b)中における、イソプレン単位の割合が、33重量%以上のものである。
分子量調整剤としては、特に限定されないが、t-ドデシルメルカプタン、n-ドデシルメルカプタン、オクチルメルカプタン等のメルカプタン類;四塩化炭素、塩化メチレン、臭化メチレン等のハロゲン化炭化水素;α-メチルスチレンダイマー;テトラエチルチウラムダイサルファイド、ジペンタメチレンチウラムダイサルファイド、ジイソプロピルキサントゲンダイサルファイド等の含硫黄化合物等が挙げられる。これらは単独で、または2種類以上を組み合わせて使用することができる。なかでも、メルカプタン類が好ましく、t-ドデシルメルカプタンがより好ましい。分子量調整剤の使用量は、全単量体100重量部に対して、好ましくは0.1~0.8重量部である。
本発明の架橋性ゴム組成物は、上記本発明のニトリル基含有高飽和共重合体ゴムと、架橋剤と、を含有してなるものである。なお、本発明の架橋性ゴム組成物は、上記本発明のニトリル基含有高飽和共重合体ゴムとして、2種以上のニトリル基含有高飽和共重合体ゴムを含有していてもよく、たとえば、ニトリル基含有高飽和共重合体ゴムを構成する単量体単位の種類や含有割合の異なるものを適宜、組み合わせて用いることができる。一例を挙げると、耐寒性と、耐油中膨潤性とを高度にバランスさせるという観点より、α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)として、炭素数1~18のアルキル基を有する(メタ)アクリル酸エステルを含有するものと、炭素数2~18のアルコキシアルキル基を有する(メタ)アクリル酸エステルを含有するものとを組み合わせて用いることができる。
また、R1およびR2は、置換基を有していないことが好ましい。
また、R3およびR4は、置換基を有していないことが好ましい。
グアニジン系塩基性架橋促進剤としては、テトラメチルグアニジン、テトラエチルグアニジン、ジフェニルグアニジン、1,3-ジ-オルト-トリルグアニジン、オルトトリルビグアニドなどが挙げられる。
アルデヒドアミン系塩基性架橋促進剤としては、n-ブチルアルデヒドアニリン、アセトアルデヒドアンモニアなどが挙げられる。
シランカップリング剤としては特に限定されないが、その具体例としては、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトメチルトリメトキシラン、γ-メルカプトメチルトリエトキシラン、γ-メルカプトヘキサメチルジシラザン、ビス(3-トリエトキシシリルプロピル)テトラスルファン、ビス(3-トリエトキシシリルプロピルジスルファンなどの硫黄を含有するシランカップリング剤;γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン等のエポキシ基含有シランカップリング剤;N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプリピルトリメトキシシラン等のアミノ基含有シランカップリング剤;γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリス(β-メトキシエトキシ)シラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-メタクリロキシプロピルメチルジエトキシシラン、γ-メタクリロキシプロピルトリエトキシシラン、γ-アクリロキシプロピルトリメトキシシラン等の(メタ)アクリロキシ基含有シランカップリング剤;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(β-メトキシエトキシ)シラン、ビニルトリクロロシラン、ビニルトリアセトキシシラン等のビニル基含有シランカップリング剤;3-クロロプロピルトリメトキシシラン等のクロロプロピル基含有シランカプリング剤;3-イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカプリング剤;p-スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤;3-ウレイドプロピルトリエトキシシラン等のウレイド基含有シランカップリング剤;ジアリルジメチルシラン等のアリル基含有シランカップリング剤;テトラエトキシシラン等のアルコキシ基含有シランカップリング剤;ジフェニルジメトキシシラン等のフェニル基含有シランカップリング剤;トリフルオロプロピルトリメトキシシラン等のフロロ基含有シランカップリング剤;イソブチルトリメトキシシラン、シクロヘキシルメチルジメトキシシラン等のアルキル基含有シランカップリング剤;などが挙げられる。
アルミニウム系カップリング剤としては特に限定されないが、その具体例としては、アセトアルコキシアルミニウムジイソポロピレートなどが挙げられる。
チタネート系カップリング剤としては特に限定されないが、その具体例としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、イソプロピルトリ(N-アミノエチル-アミノエチル)チタネート、テトラオクチルビス(ジトリデシルホスファイト)チタネート、テトラ(2,2-ジアリルオキシメチル-1-ブチル)ビス(ジトリデジル)ホスファイトチタネート、ビス(ジオクチルパイロホスフェート)オキシアセテートチタネート、ビス(ジオクチルパイロホスフェート)エチレンチタネート、テトライソプロピルビス(ジオクチルホスファイト)チタネート、イソプロピルトリイソステアロイルチタネートなどが挙げられる。これらのシランカップリング剤、アルミニウム系カップリング剤、チタネート系カップリング剤などは1種または複数種併せて用いることができる。
このようなゴムとしては、アクリルゴム、エチレン-アクリル酸共重合体ゴム、スチレン-ブタジエン共重合体ゴム、ポリブタジエンゴム、エチレン-プロピレン共重合体ゴム、エチレン-プロピレン-ジエン三元共重合体ゴム、エピクロロヒドリンゴム、フッ素ゴム、ウレタンゴム、クロロプレンゴム、シリコーンゴム、天然ゴム、ポリイソプレンゴムなどが挙げられる。
本発明のゴム架橋物は、上述した本発明の架橋性ゴム組成物を架橋してなるものである。
本発明のゴム架橋物は、本発明の架橋性ゴム組成物を用い、所望の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、加熱することにより架橋反応を行い、架橋物として形状を固定化することにより製造することができる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10~200℃、好ましくは25~120℃である。架橋温度は、通常、100~200℃、好ましくは130~190℃であり、架橋時間は、通常、1分~24時間、好ましくは2分~1時間である。
加熱方法としては、プレス加熱、スチーム加熱、オーブン加熱、熱風加熱などのゴムの架橋に用いられる一般的な方法を適宜選択すればよい。
このため、本発明のゴム架橋物は、このような特性を活かし、O-リング、パッキン、ダイアフラム、オイルシール、シャフトシール、ベアリングシール、ウェルヘッドシール、ショックアブソーバシール、空気圧機器用シール、エアコンディショナの冷却装置や空調装置の冷凍機用コンプレッサに使用されるフロン若しくはフルオロ炭化水素または二酸化炭素の密封用シール、精密洗浄の洗浄媒体に使用される超臨界二酸化炭素または亜臨界二酸化炭素の密封用シール、転動装置(転がり軸受、自動車用ハブユニット、自動車用ウォーターポンプ、リニアガイド装置およびボールねじ等)用のシール、バルブおよびバルブシート、BOP(Blow Out Preventer)、プラターなどの各種シール材;インテークマニホールドとシリンダヘッドとの連接部に装着されるインテークマニホールドガスケット、シリンダブロックとシリンダヘッドとの連接部に装着されるシリンダヘッドガスケット、ロッカーカバーとシリンダヘッドとの連接部に装着されるロッカーカバーガスケット、オイルパンとシリンダブロックあるいはトランスミッションケースとの連接部に装着されるオイルパンガスケット、正極、電解質板および負極を備えた単位セルを挟み込む一対のハウジング間に装着される燃料電池セパレーター用ガスケット、ハードディスクドライブのトップカバー用ガスケットなどの各種ガスケット;印刷用ロール、製鉄用ロール、製紙用ロール、工業用ロール、事務機用ロールなどの各種ロール;平ベルト(フィルムコア平ベルト、コード平ベルト、積層式平ベルト、単体式平ベルト等)、Vベルト(ラップドVベルト、ローエッジVベルト等)、Vリブドベルト(シングルVリブドベルト、ダブルVリブドベルト、ラップドVリブドベルト、背面ゴムVリブドベルト、上コグVリブドベルト等)、CVT用ベルト、タイミングベルト、歯付ベルト、コンベアーベルト、などの各種ベルト;燃料ホース、ターボエアーホース、オイルホース、ラジェターホース、ヒーターホース、ウォーターホース、バキュームブレーキホース、コントロールホース、エアコンホース、ブレーキホース、パワーステアリングホース、エアーホース、マリンホース、ライザー、フローラインなどの各種ホース;CVJブーツ、プロペラシャフトブーツ、等速ジョイントブーツ、ラックアンドピニオンブーツなどの各種ブーツ;クッション材、ダイナミックダンパ、ゴムカップリング、空気バネ、防振材、クラッチフェーシング材などの減衰材ゴム部品;ダストカバー、自動車内装部材、摩擦材、タイヤ、被覆ケーブル、靴底、電磁波シールド、フレキシブルプリント基板用接着剤等の接着剤、燃料電池セパレーターの他、エレクトロニクス分野など幅広い用途に使用することができる。
2mm角のニトリル基含有高飽和共重合体ゴム0.2gに、2-ブタノン100mLを加えて16時間攪拌した後、エタノール20mLおよび水10mLを加え、攪拌しながら水酸化カリウムの0.02N含水エタノール溶液を用いて、室温でチモールフタレインを指示薬とする滴定により、ゴム100gに対するカルボキシル基のモル数として求めた(単位はephr)。
ニトリル基含有高飽和共重合体ゴムのヨウ素価は、JIS K 6235に準じて測定した。
ニトリル基含有高飽和共重合体ゴムを構成する各単量体単位の含有割合は、以下の方法により測定した。
すなわち、マレイン酸モノn-ブチル単位の含有割合は、上記「カルボキシル基含有量」の測定方法により、水素化後のニトリル基含有高飽和共重合体ゴム100gに対するカルボキシル基のモル数を求め、求めたモル数をマレイン酸モノn-ブチル単位の量に換算することにより算出した。
1,3-ブタジエン単位(水素化された部分も含む)およびイソプレン単位(水素化された部分も含む)の含有割合は、次の方法により測定した。すなわち、まず、水素添加反応前のニトリル基含有高飽和共重合体ゴムのヨウ素価を上記方法で測定することにより、これらの合計含有量を算出し、次いで、1H-NMR測定を行うことで、これらの重量比率を求めることにより測定した。
アクリロニトリル単位の含有割合は、JIS K6384に従い、ケルダール法により、水素化後のニトリル基含有高飽和共重合体ゴム中の窒素含量を測定することにより算出した。
アクリル酸メトキシエチル単位およびアクリル酸n-ブチル単位の含有割合は、上記各単量体単位の残部として算出した。
架橋性ゴム組成物を、縦15cm、横15cm、深さ0.2cmの金型に入れ、プレス圧10MPaで加圧しながら170℃で20分間プレス成形してシート状の架橋物を得た。次いで、得られた架橋物をギヤー式オーブンに移して170℃で4時間または150℃で4時間二次架橋することで、シート状のゴム架橋物を作製した。JIS K6258に従い、得られたシート状のゴム架橋物を40℃に調整した試験燃料油(Fuel C:イソオクタン:トルエン=50:50(体積比率)の混合物である。)に、168時間浸漬することにより、耐油中膨潤性試験を行った。
なお、耐油中膨潤性試験においては、燃料油浸漬前後のゴム架橋物の体積を測定し、燃料油浸漬後の体積膨潤度ΔV(単位:%)を、「ΔV=([燃料油浸漬後の体積-燃料油浸漬前の体積]/燃料油浸漬前の体積)×100」に従って算出し、算出した体積膨潤度ΔVにより評価した。体積膨潤度ΔVが小さいほど、耐油中膨潤性に優れる。
上記耐油中膨潤性試験と同様にして、シート状のゴム架橋物を作製した。また、これとは別に、Fuel C(イソオクタン:トルエン=50:50(体積比率)の混合物である。)と、エタノールとの混合液(Fuel C:エタノール=80:20(体積比率))に、フェナントレン10重量%を溶解させることにより、フェナントレン含有試験燃料油を調製した。
そして、上記にて得られたシート状のゴム架橋物について、JIS K6253に従い、国際ゴム硬さ試験機(IRDH法)を用いて、硬さの測定を行った。次いで、上記にて調製したフェナントレン含有試験燃料油に、上記にて得られたシート状のゴム架橋物を、60℃、168時間浸漬させた後、ゴム架橋物をフェナントレン含有試験燃料油から取り出して、120℃で3時間乾燥し、さらに室温条件下で24時間静置した後に、上記同様の条件にて、再度、硬さの測定を行った。そして、「硬さ変化ΔHs=燃料油浸漬後の硬さ-燃料油浸漬前の硬さ」に従って、硬さ変化ΔHsを求めた。硬さ変化ΔHsの絶対値が小さいほど、試験燃料油に浸漬することによる硬度の上昇が小さく、耐油中硬化性に優れると判断できる。
上記耐油中膨潤性試験と同様にして、シート状のゴム架橋物を得て、JIS K6261に従い、TR試験(低温弾性回復試験)によりゴム架橋物の耐寒性を測定した。具体的には、伸長させたゴム架橋物を凍結させ、温度を連続的に上昇させることによって伸長されていたゴム架橋物の回復性を測定し、昇温により試験片の長さが10%収縮(回復)した時の温度TR10を測定した。TR10が低いほど、耐寒性に優れると判断できる。
反応器に、イオン交換水180部、濃度10%のドデシルベンゼンスルホン酸ナトリウム水溶液25部、アクリロニトリル43部、マレイン酸モノn-ブチル4.5部、およびt-ドデシルメルカプタン(分子量調整剤)0.75部の順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン34部およびイソプレン18.5部を仕込んだ。そして、反応器を10℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.1部、還元剤、およびキレート剤適量を仕込み、攪拌しながら重合反応を継続し、重合転化率が80%になった時点で、濃度10重量%のハイドロキノン水溶液(重合停止剤)0.1部を加えて重合反応を停止した。次いで、水温60℃で残留単量体を除去し、ニトリル基含共重合体ゴム(X1)のラテックス(固形分濃度25重量%)を得た。
重合に用いる単量体の種類および配合量を、表1および表2に示すように変更した以外は、製造例1と同様にして、ニトリル基含有高飽和共重合体ゴム(n2)~(n26)を得た。得られたニトリル基含有高飽和共重合体ゴム(n2)~(n26)のヨウ素価および単量体組成を表1および表2に示す。なお、重合反応の重合転化率および水素添加反応のパラジウム触媒量については、表1および表2に示すようなものに変更した。
また、アクリル酸メトキシエチルまたはアクリル酸n-ブチルを配合する場合における、アクリル酸メトキシエチルまたはアクリル酸n-ブチルの添加タイミングは、アクリロニトリルの添加後に、アクリル酸メトキシエチルまたはアクリル酸n-ブチルと、マレイン酸モノn-ブチルとをこの順に添加する形とした。
バンバリーミキサを用いて、製造例1で得られたニトリル基含有高飽和共重合体ゴム(n1)100部に、FEFカーボン(商品名「シーストSO」、東海カーボン社製、カーボンブラック)50部、トリメリット酸トリ-2-エチルヘキシル(商品名「アデカサイザー C-8」、ADEKA社製、可塑剤)1部、トリメリット酸イソノニルエステル(商品名「アデカサイザー C-9N」、ADEKA社製)1部、ポリエーテルエステル系可塑剤(商品名「アデカサイザー RS-700」、ADEKA社製)1部、ポリエーテルエステル系可塑剤(商品名「アデカサイザー RS-735」、ADEKA社製)1部、アジピン酸エーテルエステル系可塑剤(商品名「アデカサイザー RS-107」、ADEKA社製)1部、ステアリン酸1部、ポリオキシエチレンアルキルエーテルリン酸エステル(商品名「フォスファノールRL210」、東邦化学工業社製、加工助剤)1部、および、4,4’-ジ-(α,α’-ジメチルベンジル)ジフェニルアミン(商品名「ノクラックCD」、大内振興化学社製、老化防止剤)1.5部を添加して混練し、次いで、混合物をロールに移して1,8-ジアザビシクロ[5,4,0]ウンデセン-7(DBU)(商品名:「RHENOGRAN XLA-60(GE2014)」、RheinChemie社製、DBU重量60%(ジンクジアルキルジフォスフェイト塩になっている部分を含む)、および、アクリル酸ポリマーと分散剤40重量%からなるもの、塩基性架橋促進剤)4部、および、ヘキサメチレンジアミンカルバメート(商品名「Diak#1」、デュポン社製、脂肪族多価アミン類に属するポリアミン系架橋剤)2.0部を添加して混練することで、架橋性ゴム組成物を得た。
製造例1で得られたニトリル基含有高飽和共重合体ゴム(n1)に代えて、製造例2~9で得られたニトリル基含有高飽和共重合体ゴム(n2)~(n9)を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表1に示す。なお、架橋剤としてのヘキサメチレンジアミンカルバメートの配合量はマレイン酸モノn-ブチル単位に比例して変量させた。
バンバリーミキサを用いて、製造例10で得られたニトリル基含有高飽和共重合体ゴム(n10)100部に、FEFカーボン(商品名「シーストSO」、東海カーボン社製、カーボンブラック)50部、トリメリット酸トリ-2-エチルヘキシル(商品名「アデカサイザー C-8」、ADEKA社製、可塑剤)1部、トリメリット酸イソノニルエステル(商品名「アデカサイザー C-9N」、ADEKA社製)1部、ポリエーテルエステル系可塑剤(商品名「アデカサイザー RS-700」、ADEKA社製)1部、ポリエーテルエステル系可塑剤(商品名「アデカサイザー RS-735」、ADEKA社製)1部、アジピン酸エーテルエステル系可塑剤(商品名「アデカサイザー RS-107」、ADEKA社製)1部、ステアリン酸(架橋促進助剤)1部、酸化亜鉛(亜鉛華2種、正同化学社製)5部、4,4’-ジ-(α,α’-ジメチルベンジル)ジフェニルアミン(商品名「ノクラックCD」、大内振興化学社製、老化防止剤)1.5部、および、2-メルカプトベンズイミダゾールの亜鉛塩(商品名「ノクラック MBZ」、大内振興化学社製、老化防止剤)1.5部を添加して混練し、次いで、混合物をロールに移して1,3-ビス(t-ブチルパーオキシイソプロピル)ベンゼン(40%品)(商品名「バルカップ40KE」、アルケマ社製、有機過酸化物架橋剤)8.0部を添加して混練することで、架橋性ゴム組成物を得た。
製造例10で得られたニトリル基含有高飽和共重合体ゴム(n10)に代えて、製造例11~18で得られたニトリル基含有高飽和共重合体ゴム(n11)~(n18)を使用した以外は、実施例10と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表1、表2に示す。
製造例1で得られたニトリル基含有高飽和共重合体ゴム(n1)に代えて、製造例19~21で得られたニトリル基含有高飽和共重合体ゴム(n19)~(n21)を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表2に示す。なお、架橋剤としてのヘキサメチレンジアミンカルバメートの配合量はマレイン酸モノn-ブチル単位に比例して変量させた。
製造例10で得られたニトリル基含有高飽和共重合体ゴム(n10)に代えて、製造例22~26で得られたニトリル基含有高飽和共重合体ゴム(n22)~(n26)を使用した以外は、実施例10と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表2に示す。
また、α,β-エチレン性不飽和ニトリル単量体単位(a)の含有割合が少なすぎる場合には、得られるゴム架橋物は、油中における体積変化が大きくなり、耐油中膨潤性に劣るものであった(比較例3,8)。
Claims (9)
- α,β-エチレン性不飽和ニトリル単量体単位(a)28重量%以上、および共役ジエン単量体単位(b)20~72重量%を含有し、ヨウ素価が120以下であるニトリル基含有高飽和共重合体ゴムであって、
前記共役ジエン単量体単位(b)は、少なくとも一部は水素化されており、前記共役ジエン単量体単位(b)中における、イソプレン単位の割合が、33重量%以上であるニトリル基含有高飽和共重合体ゴム。 - 前記共役ジエン単量体単位(b)として、イソプレン単位と、1,3-ブタジエン単位とを含有する請求項1に記載のニトリル基含有高飽和共重合体ゴム。
- α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)をさらに含有する請求項1または2に記載のニトリル基含有高飽和共重合体ゴム。
- 前記α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)が、炭素数1~18のアルキル基を有する(メタ)アクリル酸エステルである請求項3に記載のニトリル基含有高飽和共重合体ゴム。
- 前記α,β-エチレン性不飽和モノカルボン酸エステル単量体単位(c)が、炭素数2~18のアルコキシアルキル基を有する(メタ)アクリル酸エステルである請求項3に記載のニトリル基含有高飽和共重合体ゴム。
- カルボキシル基含有単量体単位(d)をさらに含有する請求項1~5のいずれかに記載のニトリル基含有高飽和共重合体ゴム。
- 前記カルボキシル基含有単量体単位(d)が、α,β-エチレン性不飽和ジカルボン酸モノエステル単量体単位である請求項1~5のいずれかに記載のニトリル基含有高飽和共重合体ゴム。
- 請求項1~7のいずれかに記載のニトリル基含有高飽和共重合体ゴムと、架橋剤とを含有してなる架橋性ゴム組成物。
- 請求項8に記載の架橋性ゴム組成物を架橋してなるゴム架橋物。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16799920.0A EP3305818A4 (en) | 2015-05-26 | 2016-05-19 | Nitrile group containing, highly saturated copolymer rubber |
MX2017014732A MX2017014732A (es) | 2015-05-26 | 2016-05-19 | Caucho de copolimero altamente saturado que contiene grupo nitrilo. |
US15/574,595 US10752717B2 (en) | 2015-05-26 | 2016-05-19 | Nitrile group-containing highly saturated copolymer rubber |
JP2017520663A JP6741002B2 (ja) | 2015-05-26 | 2016-05-19 | ニトリル基含有高飽和共重合体ゴム |
CA2986209A CA2986209A1 (en) | 2015-05-26 | 2016-05-19 | Nitrile group-containing highly saturated copolymer rubber |
CN201680027917.8A CN107614552B (zh) | 2015-05-26 | 2016-05-19 | 含腈基高饱和共聚物橡胶 |
KR1020177033640A KR102500518B1 (ko) | 2015-05-26 | 2016-05-19 | 니트릴기 함유 고포화 공중합체 고무 |
BR112017024682-1A BR112017024682B1 (pt) | 2015-05-26 | 2016-05-19 | Borracha de copolímero altamente saturado contendo grupo nitrila, composição de borracha reticulável, e, borracha reticulada |
RU2017140074A RU2017140074A (ru) | 2015-05-26 | 2016-05-19 | Высоконасыщенный сополимерный каучук, содержащий нитрильные группы |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-106186 | 2015-05-26 | ||
JP2015106186 | 2015-05-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016190214A1 true WO2016190214A1 (ja) | 2016-12-01 |
Family
ID=57393306
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/064876 WO2016190214A1 (ja) | 2015-05-26 | 2016-05-19 | ニトリル基含有高飽和共重合体ゴム |
Country Status (10)
Country | Link |
---|---|
US (1) | US10752717B2 (ja) |
EP (1) | EP3305818A4 (ja) |
JP (1) | JP6741002B2 (ja) |
KR (1) | KR102500518B1 (ja) |
CN (1) | CN107614552B (ja) |
BR (1) | BR112017024682B1 (ja) |
CA (1) | CA2986209A1 (ja) |
MX (1) | MX2017014732A (ja) |
RU (1) | RU2017140074A (ja) |
WO (1) | WO2016190214A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019078068A1 (ja) * | 2017-10-17 | 2019-04-25 | Nok株式会社 | 水素化nbr組成物 |
WO2021090748A1 (ja) * | 2019-11-05 | 2021-05-14 | 日本ゼオン株式会社 | ニトリル基含有共重合体ゴム |
JP2021519370A (ja) * | 2018-04-19 | 2021-08-10 | アランセオ・ドイチュランド・ゲーエムベーハー | 冷却剤と接触状態にある、hnbr−pegアクリレートコポリマーを含む加硫物の使用 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11512187B2 (en) | 2017-12-26 | 2022-11-29 | Zeon Corporation | Rubber composition and rubber crosslinked product |
CN117561385A (zh) * | 2021-05-24 | 2024-02-13 | 戴科欧洲有限公司 | 传动带 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04261407A (ja) * | 1990-08-15 | 1992-09-17 | Bayer Ag | 共重合体の水素化方法及び該水素化物 |
JPH08104778A (ja) * | 1995-09-25 | 1996-04-23 | Nippon Zeon Co Ltd | ゴム材料 |
JPH10152525A (ja) * | 1996-09-27 | 1998-06-09 | Nippon Zeon Co Ltd | カルボキシル化ニトリル基含有高飽和共重合体ゴム |
WO1998044039A1 (fr) * | 1997-03-31 | 1998-10-08 | Nippon Zeon Co., Ltd. | Composition comportant un melange de resine synthetique et de caoutchouc copolymere de nitrile, carboxyle et hautement sature |
JP2004506087A (ja) * | 2000-08-25 | 2004-02-26 | バイエル・インコーポレーテツド | 改良された低温特性を有する水素化ニトリルゴム |
JP2004190030A (ja) * | 2002-12-05 | 2004-07-08 | Bayer Inc | 低分子量水素化ニトリルゴムの製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4795504B2 (ja) * | 1999-10-15 | 2011-10-19 | 日本ゼオン株式会社 | ゴム、ゴム組成物および架橋物 |
EP2292667B1 (en) | 2008-06-27 | 2013-02-20 | Zeon Corporation | Nitrile group-containing highly saturated copolymer rubber |
WO2010087431A1 (ja) * | 2009-01-30 | 2010-08-05 | 日本ゼオン株式会社 | ニトリル基含有高飽和共重合体ゴム |
JP5510218B2 (ja) * | 2010-09-13 | 2014-06-04 | 日本ゼオン株式会社 | ニトリル基含有高飽和共重合体ゴム組成物 |
EP2660285B1 (en) * | 2010-12-27 | 2016-05-25 | Zeon Corporation | Rubber composition and crosslinked rubber product |
EP2891694B1 (en) * | 2012-08-31 | 2018-06-06 | Zeon Corporation | Adhesive agent composition |
CA2986208A1 (en) | 2015-05-26 | 2016-12-01 | Zeon Corporation | Nitrile group-containing highly saturated copolymer rubber |
-
2016
- 2016-05-19 CN CN201680027917.8A patent/CN107614552B/zh active Active
- 2016-05-19 JP JP2017520663A patent/JP6741002B2/ja active Active
- 2016-05-19 US US15/574,595 patent/US10752717B2/en active Active
- 2016-05-19 WO PCT/JP2016/064876 patent/WO2016190214A1/ja active Application Filing
- 2016-05-19 KR KR1020177033640A patent/KR102500518B1/ko active IP Right Grant
- 2016-05-19 MX MX2017014732A patent/MX2017014732A/es unknown
- 2016-05-19 BR BR112017024682-1A patent/BR112017024682B1/pt active IP Right Grant
- 2016-05-19 EP EP16799920.0A patent/EP3305818A4/en active Pending
- 2016-05-19 RU RU2017140074A patent/RU2017140074A/ru not_active Application Discontinuation
- 2016-05-19 CA CA2986209A patent/CA2986209A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04261407A (ja) * | 1990-08-15 | 1992-09-17 | Bayer Ag | 共重合体の水素化方法及び該水素化物 |
JPH08104778A (ja) * | 1995-09-25 | 1996-04-23 | Nippon Zeon Co Ltd | ゴム材料 |
JPH10152525A (ja) * | 1996-09-27 | 1998-06-09 | Nippon Zeon Co Ltd | カルボキシル化ニトリル基含有高飽和共重合体ゴム |
WO1998044039A1 (fr) * | 1997-03-31 | 1998-10-08 | Nippon Zeon Co., Ltd. | Composition comportant un melange de resine synthetique et de caoutchouc copolymere de nitrile, carboxyle et hautement sature |
JP2004506087A (ja) * | 2000-08-25 | 2004-02-26 | バイエル・インコーポレーテツド | 改良された低温特性を有する水素化ニトリルゴム |
JP2004190030A (ja) * | 2002-12-05 | 2004-07-08 | Bayer Inc | 低分子量水素化ニトリルゴムの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3305818A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019078068A1 (ja) * | 2017-10-17 | 2019-04-25 | Nok株式会社 | 水素化nbr組成物 |
JP2021519370A (ja) * | 2018-04-19 | 2021-08-10 | アランセオ・ドイチュランド・ゲーエムベーハー | 冷却剤と接触状態にある、hnbr−pegアクリレートコポリマーを含む加硫物の使用 |
JP7440421B2 (ja) | 2018-04-19 | 2024-02-28 | アランセオ・ドイチュランド・ゲーエムベーハー | 冷却剤と接触状態にある、hnbr-pegアクリレートコポリマーを含む加硫物の使用 |
WO2021090748A1 (ja) * | 2019-11-05 | 2021-05-14 | 日本ゼオン株式会社 | ニトリル基含有共重合体ゴム |
CN114555660A (zh) * | 2019-11-05 | 2022-05-27 | 日本瑞翁株式会社 | 含腈基共聚物橡胶 |
EP4056601A4 (en) * | 2019-11-05 | 2023-11-29 | Zeon Corporation | COPOLYMER RUBBER CONTAINING NITRILE GROUPS |
CN114555660B (zh) * | 2019-11-05 | 2024-06-11 | 日本瑞翁株式会社 | 含腈基共聚物橡胶 |
Also Published As
Publication number | Publication date |
---|---|
BR112017024682B1 (pt) | 2022-04-26 |
US10752717B2 (en) | 2020-08-25 |
KR102500518B1 (ko) | 2023-02-15 |
RU2017140074A3 (ja) | 2019-11-13 |
EP3305818A4 (en) | 2018-10-24 |
RU2017140074A (ru) | 2019-06-26 |
US20180127530A1 (en) | 2018-05-10 |
CA2986209A1 (en) | 2016-12-01 |
EP3305818A1 (en) | 2018-04-11 |
KR20180011770A (ko) | 2018-02-02 |
CN107614552B (zh) | 2021-06-15 |
JP6741002B2 (ja) | 2020-08-19 |
JPWO2016190214A1 (ja) | 2018-03-08 |
BR112017024682A2 (ja) | 2018-07-24 |
MX2017014732A (es) | 2018-08-01 |
CN107614552A (zh) | 2018-01-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11091577B2 (en) | Nitrile group-containing highly saturated copolymer rubber | |
JP6601407B2 (ja) | 架橋性ニトリルゴム組成物およびゴム架橋物 | |
WO2017047571A1 (ja) | ニトリルゴム組成物、架橋性ニトリルゴム組成物およびゴム架橋物 | |
WO2017010370A1 (ja) | ニトリルゴム組成物およびゴム架橋物 | |
WO2016148055A1 (ja) | ニトリルゴム組成物およびゴム架橋物 | |
JP6741002B2 (ja) | ニトリル基含有高飽和共重合体ゴム | |
WO2017119424A1 (ja) | ニトリルゴム組成物、架橋性ニトリルゴム組成物およびゴム架橋物 | |
US11286324B2 (en) | Carboxyl group-containing nitrile rubber, method for production same, crosslinkable nitrile rubber composition, and crosslinked rubber | |
WO2018168395A1 (ja) | ニトリル基含有共重合体ゴム | |
JP6733658B2 (ja) | ニトリルゴム組成物およびゴム架橋物 | |
CN110461892B (zh) | 含腈基共聚物橡胶 | |
WO2018198998A1 (ja) | ゴム架橋物の製造方法 | |
WO2021090748A1 (ja) | ニトリル基含有共重合体ゴム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16799920 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017520663 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2986209 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15574595 Country of ref document: US Ref document number: MX/A/2017/014732 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 20177033640 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017140074 Country of ref document: RU |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112017024682 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112017024682 Country of ref document: BR Kind code of ref document: A2 Effective date: 20171117 |