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WO2018151163A1 - Composition de polymère, produit réticulé et corps moulé obtenus au moyen de cette composition - Google Patents

Composition de polymère, produit réticulé et corps moulé obtenus au moyen de cette composition Download PDF

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Publication number
WO2018151163A1
WO2018151163A1 PCT/JP2018/005112 JP2018005112W WO2018151163A1 WO 2018151163 A1 WO2018151163 A1 WO 2018151163A1 JP 2018005112 W JP2018005112 W JP 2018005112W WO 2018151163 A1 WO2018151163 A1 WO 2018151163A1
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Prior art keywords
group
cationic group
polyether compound
polymer composition
weight
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PCT/JP2018/005112
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English (en)
Japanese (ja)
Inventor
弘康 永森
篤史 高柳
重孝 早野
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日本ゼオン株式会社
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Priority to JP2018568574A priority Critical patent/JP7103236B2/ja
Publication of WO2018151163A1 publication Critical patent/WO2018151163A1/fr

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    • 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
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • 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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics

Definitions

  • the present invention provides a polymer composition capable of providing a crosslinked product and a molded article having excellent mechanical properties and excellent barrier properties against gases and liquids, and such a polymer composition.
  • the present invention relates to a crosslinked product and a molded product.
  • polymer materials are used in a wide range of products, they are required to have high barrier properties (specifically, gas barrier properties and fuel permeation resistance) depending on the intended use.
  • barrier properties specifically, gas barrier properties and fuel permeation resistance
  • Patent Document 1 discloses a molded rubber composition used as a component of pneumatic equipment, which includes a nitrile rubber having a combined acrylonitrile amount of 30 to 60% by mass and a layered clay mineral. A rubber molded product obtained in this manner is disclosed.
  • the present invention has been made in view of such a situation, and is a polymer composition capable of providing a cross-linked product and a molded product having excellent mechanical properties and excellent barrier properties against gases and liquids.
  • the purpose is to provide.
  • Another object of the present invention is to provide a crosslinkable composition, a cross-linked product and a molded article obtained using such a polymer composition, and a hose containing such a cross-linked product.
  • the present inventors have found that the above object can be achieved according to a polymer composition comprising a polymer material, a polyether compound having a cationic group, and a clay mineral.
  • the headline and the present invention have been completed.
  • a polymer composition comprising a polymer material, a polyether compound having a cationic group, and a clay mineral.
  • the polyether compound having a cationic group is preferably composed of a monomer unit represented by the following general formula (1).
  • a + represents a cationic group or a cationic group-containing group
  • X ⁇ represents an arbitrary counter anion
  • R represents a nonionic group
  • n represents 2 or more.
  • the content of the polyether compound having a cationic group is preferably 0.01 to 40 parts by weight with respect to 100 parts by weight of the polymer material.
  • the clay mineral content is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the polymer material.
  • blending a crosslinking agent with said polymer composition is provided.
  • crosslinked composition is provided.
  • molding said polymer composition is provided.
  • the hose containing said crosslinked material is provided.
  • the crosslinked material and molded object which are excellent in a mechanical characteristic and are equipped with the barrier property (specifically gas barrier property and fuel-permeation resistance) with respect to gas and a liquid can be given. It is possible to provide a polymer composition, and further, a crosslinkable composition, a cross-linked product and a molded article obtained by using such a polymer composition, and a hose containing such a cross-linked product.
  • the polymer composition of the present invention is a composition comprising a polymer material, a polyether compound having a cationic group, and a clay mineral. First, each component contained in the polymer composition of the present invention will be described.
  • the polymer material used in the present invention is not particularly limited as long as it is a general polymer material, and any of resin and rubber can be used without limitation.
  • the resin may be either a thermosetting resin or a thermoplastic resin and is not particularly limited.
  • the thermosetting resin include an epoxy resin, a melamine resin, a bakelite, a urea resin, a polyurethane, and a silicone resin. .
  • thermoplastic resin examples include polyolefin resins such as polyethylene, polypropylene, polycycloolefin, and 1,2-polybutadiene; vinyl resins such as polystyrene, acrylic resin, PAN, ABS resin, AS resin, vinyl chloride, and PVA; Fluorine resin such as Teflon (registered trademark); Polyester resin such as PET and PBT; Polyamide such as nylon 66 and nylon 6, polyether (polyether compound having a cationic group represented by the general formula (1)) And other resins such as polyacetal, polycarbonate, polyimide, PEEK, polysulfone, polyethersulfone, and liquid crystal polymer. These may be used alone or in combination of two or more. Moreover, these can also be used in combination with the rubber
  • polyolefin resins such as polyethylene, polypropylene, polycycloolefin, and 1,2-polybutadiene
  • vinyl resins such as polystyrene, acrylic resin, P
  • the weight average molecular weight (Mw) of the thermoplastic resin is not particularly limited, but is preferably 20,000 to 1,000,000, more preferably 25,000 to 700,000, particularly preferably 30,000 to 500. , 000.
  • Mw weight average molecular weight
  • the weight average molecular weight of the thermoplastic resin is not particularly limited, but is preferably 20,000 to 1,000,000, more preferably 25,000 to 700,000, particularly preferably 30,000 to 500. , 000.
  • the weight average molecular weight (Mw) of the thermosetting resin is not particularly limited as long as it is cured by three-dimensional crosslinking.
  • the rubber is not particularly limited.
  • butadiene rubber styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, acrylonitrile butadiene rubber (nitrile rubber), butyl rubber, and partially hydrogenated products of these rubbers (for example, hydrogenated)
  • Various rubbers such as diene rubbers such as nitrile rubber; rubbers other than diene rubbers such as ethylene propylene rubber, acrylic rubber, polyether rubber, polyurethane rubber, fluorine rubber, and silicone rubber; can be used without limitation. These can be used alone or in combination of two or more, and further, such rubbers and the above-described resins may be used in combination.
  • the weight average molecular weight (Mw) of the rubber is not particularly limited, but is preferably 200,000 to 2,000,000, more preferably 300,000 to 2,000,000, from the viewpoint of further improving mechanical properties. 000, particularly preferably 400,000 to 1,500,000.
  • the measurement of the weight average molecular weight (Mw) of the resin and rubber used in the present invention is obtained as a polystyrene-equivalent molecular weight by gel permeation chromatography.
  • the Mooney viscosity (ML1 + 4, 100 ° C.) of the rubber is preferably 5 to 250, more preferably 10 to 200, and particularly preferably 20 to 160.
  • polycycloolefin from the viewpoint that the effect of blending the polyether compound having the cationic group represented by the general formula (1) and the clay mineral is higher, Nitrile rubber and hydrogenated nitrile rubber are preferable, and nitrile rubber and hydrogenated nitrile rubber are particularly preferable.
  • the polymer composition of the present invention is usually made into a crosslinkable composition by adding a crosslinking agent, and is crosslinked by crosslinking. It will be used as a thing.
  • nitrile rubber for example, a rubber containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a conjugated diene monomer unit can be used.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is preferably 15 to 80% by weight, more preferably 30 to 70% by weight, still more preferably 40%, based on the total monomer units. ⁇ 65% by weight.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is in the above range, the oil resistance, fuel permeation resistance and cold resistance of the resulting crosslinked product can be further improved.
  • the conjugated diene monomer forming the conjugated diene monomer unit is preferably a conjugated diene monomer having 4 to 6 carbon atoms, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3. -Butadiene, 1,3-pentadiene and the like. Of these, 1,3-butadiene is preferred. These can be used individually by 1 type or in combination of multiple types.
  • the content ratio of the conjugated diene monomer unit is preferably 20 to 85% by weight, more preferably 30 to 70% by weight, still more preferably 34.9 to 59.9% by weight based on the total monomer units. %.
  • the content ratio of the conjugated diene monomer unit is in the above range, the obtained cross-linked product can be made excellent in heat aging resistance and chemical resistance while making rubber elasticity good.
  • the nitrile rubber includes a cationic monomer unit and / or a monomer unit capable of forming a cation. May also be included.
  • a cationic monomer unit and / or a monomer unit capable of forming a cation By further containing a cationic monomer unit and / or a monomer unit capable of forming a cation, the barrier property of the resulting crosslinked product against gas or liquid can be further enhanced.
  • the monomer that forms the cationic monomer unit and / or the monomer unit capable of forming a cation is a monomer that forms a positively charged monomer unit when in contact with water or an aqueous acid solution.
  • a monomer there is no particular limitation as long as it is a monomer.
  • examples of such a monomer include a monomer containing a quaternary ammonium base as a cationic monomer.
  • a monomer capable of forming a cation it is cationized to an ammonium salt (for example, amine hydrochloride or amine sulfate) when coming into contact with an aqueous acid solution such as hydrochloric acid and sulfuric acid such as a tertiary amino group.
  • an ammonium salt for example, amine hydrochloride or amine sulfate
  • an aqueous acid solution such as hydrochloric acid and sulfuric acid such as a tertiary amino group.
  • cationic monomer examples include (meth) acryloyloxytrimethylammonium chloride [acryloyloxytrimethylammonium chloride and / or methacryloyloxytrimethylammonium chloride. The same applies hereinafter.
  • Quaternary ammonium bases such as (meth) acryloyloxyhydroxypropyltrimethylammonium chloride, (meth) acryloyloxytriethylammonium chloride, (meth) acryloyloxydimethylbenzylammonium chloride, (meth) acryloyloxytrimethylammonium methyl sulfate (Meth) acrylic acid ester monomers; (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidepropyldimethylbenzylammonium chloride and other (meth) acrylamide monomers containing quaternary ammonium bases; It is done.
  • the monomer capable of forming a cation include vinyl group-containing cyclic amine monomers such as 2-vinylpyridine and 4-vinylpyridine; tertiary amino groups such as dimethylaminoethyl (meth) acrylate.
  • (Meth) acrylic acid ester monomer (meth) acrylamide-containing (meth) acrylamide monomer such as (meth) acrylamide dimethylaminoethyl and N, N-dimethylaminopropylacrylamide; N- (4-anilinophenyl) ) Acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) ) Aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like. Of these, 2-vinylpyridine is preferred.
  • cationic monomers and monomers capable of forming cations can be used singly or in combination.
  • the content ratio of the cationic monomer unit and / or the monomer unit capable of forming a cation is preferably 30% by weight or less, more preferably 20% by weight or less, still more preferably, based on the total monomer units. 10% by weight or less.
  • it does not specifically limit about a minimum, In order to improve the barrier property with respect to the gas and liquid of the crosslinked material obtained more appropriately, Preferably it is 0.1 weight% or more.
  • the nitrile rubber can form an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, a conjugated diene monomer unit, and a cationic monomer unit and / or cation contained as necessary.
  • other monomer units copolymerizable with the monomers forming these monomer units may be contained.
  • the content ratio of such other monomer units is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less based on the total monomer units.
  • Examples of such other copolymerizable monomers include fluorine containing fluoroethyl vinyl ether, fluoropropyl vinyl ether, o- (trifluoro) methylstyrene, vinyl pentafluorobenzoate, difluoroethylene, tetrafluoroethylene and the like.
  • Vinyl compounds such as 1,4-pentadiene, 1,4-hexadiene, vinylnorbornene, dicyclopentadiene; ethylene; propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene ⁇ -olefin compounds such as octene; ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, maleic anhydride, etc.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic Acids and anhydrides thereof ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic Acids and anhydrides thereof; ⁇ , ⁇ -ethylenically unsaturated carboxylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; Monoethyl maleate, diethyl maleate, monobutyl maleate, dibutyl maleate, monoethyl fumarate, diethyl fumarate, monobutyl fumarate, dibutyl fumarate, monocyclohexyl fumarate, dicyclohexyl fumarate, monoethyl itaconate, diethyl itaconate, itacone Monoesters and diesters of ⁇ , ⁇ -e
  • polyfunctional ethylenically unsaturated monomers such as tri (meth) acrylic acid esters; self-crosslinking compounds such as N-methylol (meth) acrylamide and N, N′-dimethylol (meth) acrylamide; Can be mentioned.
  • Nitrile rubber can be produced by copolymerizing the above monomers.
  • a method for copolymerizing each monomer an emulsion polymerization method, a suspension polymerization method, or the like can be used, and among these, the emulsion polymerization method is more preferable because the polymerization reaction can be easily controlled.
  • hydrogenated nitrile rubber is obtained by hydrogenating (hydrogenating reaction) at least a part of the carbon-carbon unsaturated bond portion in the conjugated diene monomer unit portion of the obtained nitrile rubber copolymer. You can also.
  • the method for hydrogenation is not particularly limited, and a known method may be employed.
  • the iodine value is preferably 120 or less, more preferably 80 or less, and still more preferably 60 or less.
  • the polyether compound having a cationic group used in the present invention is a polymer comprising an oxirane monomer unit as a main chain, which is a unit obtained by ring-opening polymerization of an oxirane structure portion of a compound containing an oxirane structure.
  • An ether compound having a cationic group in its molecule is a polymer comprising an oxirane monomer unit as a main chain, which is a unit obtained by ring-opening polymerization of an oxirane structure portion of a compound containing an oxirane structure.
  • the polyether compound having a cationic group used in the present invention is a polymer having a main chain structure composed of oxirane monomer units and 5 to 500 oxirane monomer units, It is preferable to contain an oxirane monomer unit having a cationic group as at least a part of the monomer unit.
  • the number of oxirane monomer units is more preferably 5 to 400, and still more preferably 5 to 300.
  • oxirane monomer unit for forming the polyether compound having a cationic group used in the present invention examples include alkylene oxide monomer units such as ethylene oxide units, propylene oxide units, and 1,2-butylene oxide units; Epihalohydrin monomer units such as epichlorohydrin units, epibromohydrin units, epiiodohydrin units; alkenyl group-containing oxirane monomer units such as allyl glycidyl ether units; aromatic ether groups such as phenyl glycidyl ether units Examples thereof include, but are not limited to, containing oxirane monomer units; (meth) acryloyl group-containing oxirane monomer units such as glycidyl acrylate units and glycidyl methacrylate units.
  • the polyether compound having a cationic group used in the present invention may contain two or more oxirane monomer units.
  • the distribution pattern of the plurality of repeating units is not particularly limited. However, it is preferable to have a random distribution.
  • the epihalohydrin monomer unit, the alkenyl group-containing oxirane monomer unit, and the (meth) acryloyl group-containing oxirane monomer unit are oxirane monomer units having a crosslinkable group.
  • a crosslinkable group can be introduced in addition to the cationic group,
  • a polyether compound having a cationic group can be crosslinked by using a combination of crosslinking agents.
  • the ratio of the oxirane monomer unit having a crosslinkable group can be any ratio.
  • the oxirane monomer unit having a crosslinkable group may be a monomer unit having a crosslinkable group, and is not particularly limited to those described above. Further, in the oxirane monomer unit constituting the polyether compound having a cationic group, the cationic group and the crosslinkable group may be contained as the same repeating unit or as separate repeating units. However, it is preferably contained as a separate repeating unit.
  • the polyether compound having a cationic group used in the present invention contains an oxirane monomer unit having a cationic group as at least a part of the oxirane monomer unit.
  • the cationic group that can be contained in the polyether compound having a cationic group used in the present invention is not particularly limited, but from the viewpoint of further improving the barrier property against the gas and liquid of the resulting crosslinked product and molded product,
  • the group 15 or group 16 atom of the periodic table is preferably a cationic group having an onium cation structure, and the nitrogen atom is more preferably a cationic group having an onium cation structure.
  • cationic group examples include ammonium group, methylammonium group, butylammonium group, cyclohexylammonium group, anilinium group, benzylammonium group, ethanolammonium group, dimethylammonium group, diethylammonium group, dibutylammonium group, and nonylphenylammonium.
  • 1-methylpyrrolidinium group trimethylammonium group, n-butyldimethylammonium group, imidazolium group, 1-methylimidazolium group, 1-ethylimidazolium group, benzimidazolium group, pyridinium group, 2 1,6-dimethylpyridinium group and the like are preferable.
  • the polyether compound having a cationic group used in the present invention all the cationic groups contained may be the same, or an embodiment containing two or more different groups may be used. .
  • the cationic group usually has a counter anion, but the counter anion is not particularly limited.
  • halide ions such as fluoride ion, chloride ion, bromide ion, iodide ion; Sulfate ion; Sulphite ion; Hydroxide ion; Carbonate ion; Hydrogen carbonate ion; Nitrate ion; Acetic acid ion; Perchlorate ion; Phosphate ion; Alkyloxy ion; Trifluoromethanesulfonate ion; Hexafluorophosphate ion; tetrafluoroborate ion; and the like.
  • counter anions may be appropriately selected according to the properties of the polymer composition to be obtained.
  • the counter anions may all be the same, or may be an embodiment containing two or more different types of anions.
  • the oxirane monomer units constituting the polyether compound may be an oxirane monomer unit having a cationic group. All of the oxirane monomer units constituting the polyether compound may have a cationic group, or an oxirane monomer unit having a cationic group and an oxirane monomer having no cationic group Units may be mixed.
  • the proportion of the oxirane monomer unit having a cationic group is not particularly limited, and the oxirane monomer unit constituting the polyether compound having a cationic group 1 mol% or more is preferable with respect to the whole, 10 mol% or more is more preferable, and 30 mol% or more is especially preferable.
  • the upper limit of the ratio for which the oxirane monomer unit which has a cationic group accounts is not specifically limited. By making the ratio which the oxirane monomer unit which has a cationic group accounts to the said range, the barrier property with respect to the gas and liquid of the crosslinked material and molded object which are obtained can be improved more.
  • a + represents a cationic group or a cationic group-containing group
  • X ⁇ represents an arbitrary counter anion
  • R represents a nonionic group
  • n represents 2 or more.
  • It is an integer
  • m is an integer of 0 or more
  • n + m is an integer of 5 to 500.
  • a + represents a cationic group or a cationic group-containing group, and specific examples of the cationic group include those described above.
  • the group containing the cationic group mentioned above is mentioned.
  • the cationic groups or the cationic group-containing groups represented by A + may all be the same, or may contain two or more different groups. There may be.
  • X ⁇ represents an arbitrary counter anion.
  • specific examples of the counter anion include those described above.
  • the counter anions represented by X ⁇ may all be the same or may contain two or more different types of anions.
  • R is a nonionic group and is not particularly limited as long as it is a nonionic group.
  • R is, for example, a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group; a vinyl group, an allyl group Groups, alkenyl groups having 2 to 10 carbon atoms such as propenyl groups; alkynyl groups having 2 to 10 carbon atoms such as ethynyl groups and propynyl groups; and 3 to 20 carbon atoms such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, etc.
  • Cycloalkyl groups aryl groups having 6 to 20 carbon atoms such as phenyl, 1-naphthyl and 2-naphthyl groups; and the like.
  • an alkyl group having 1 to 10 carbon atoms an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms May have a substituent at any position.
  • substituents examples include an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; and a carbon number such as a vinyloxy group and an allyloxy group 2-6 alkenyloxy groups; aryl groups optionally having substituents such as phenyl group, 4-methylphenyl group, 2-chlorophenyl group, 3-methoxyphenyl group; fluorine atom, chlorine atom, bromine atom, etc.
  • a C 1-6 alkylcarbonyl group such as a methylcarbonyl group or an ethylcarbonyl group; a (meth) acryloyloxy group such as an acryloyloxy group or a methacryloyloxy group;
  • R when there are a plurality of nonionic groups represented by R, they may all be the same, or may contain two or more different groups. It may be.
  • n is an integer of 2 or more
  • m may be an integer of 0 or more, but n is preferably an integer of 2 to 500, and an integer of 2 to 400 Is more preferable, an integer of 3 to 300 is more preferable, and an integer of 50 to 300 is particularly preferable.
  • M is preferably an integer of 0 to 498, more preferably an integer of 0 to 398, still more preferably an integer of 0 to 297, and particularly preferably an integer of 0 to 250.
  • N + m is an integer of 5 to 500, more preferably an integer of 5 to 400, still more preferably an integer of 5 to 300, and particularly preferably an integer of 50 to 300.
  • compatibility with the polymer material and affinity with the clay mineral can be adjusted, and in particular, n, m and n + m are By setting the range, the compatibility with the polymer material and the affinity with the clay mineral can be improved satisfactorily, thereby further improving the mechanical properties and the barrier property against gas and liquid of the resulting crosslinked product and molded product. Can be raised appropriately.
  • the polymer chain end is not particularly limited, It can be any group.
  • the polymer chain end group include the above-described cationic group, hydroxyl group, or hydrogen atom.
  • the synthesis method of the polyether compound having a cationic group used in the present invention is not particularly limited, and any synthesis method can be adopted as long as the target compound can be obtained.
  • a base polymer polyether compound having no cationic group
  • JP-A 2010-53217 discloses a monomer containing an oxirane monomer including at least an epihalohydrin such as epichlorohydrin, epibromohydrin, epiiohydrin, etc. as a catalyst.
  • a catalyst comprising an onium salt of a compound containing a group 15 or 16 atom of the periodic table and a trialkylaluminum in which all of the alkyl groups contained are linear alkyl groups.
  • a method of obtaining a base polymer by ring-opening polymerization (B) A monomer containing an oxirane monomer including at least an epihalohydrin such as epichlorohydrin, epibromohydrin, epiiodohydrin, etc. is disclosed in JP-B-46-27534.
  • a method for obtaining a base polymer by ring-opening polymerization in the presence of a catalyst obtained by reacting phosphoric acid and triethylamine with isobutylaluminum.
  • a polyether compound having a cationic group can be obtained by performing an anion exchange reaction on the halide ions constituting the onium halide group, if necessary.
  • the content of the polyether compound having a cationic group in the polymer composition of the present invention is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer material. Parts, more preferably 0.2 to 10 parts by weight.
  • the clay mineral used in the present invention is not particularly limited, and may be derived from a natural product, a product obtained by subjecting a natural product to a treatment such as purification, or a synthetic product.
  • the clay mineral used in the present invention usually has a layered or plate-like shape.
  • the clay mineral used in the present invention include kaolinites such as kaolinite and halosite; smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, mica; and vermiculites; Among them, smectites are preferable, and montmorillonite, mica, and saponite are particularly preferable. These can be used individually by 1 type or in combination of multiple types.
  • montmorillonite is contained as a main component in bentonite. Therefore, as montmorillonite, those obtained by purifying bentonite can be used.
  • the content of the clay mineral in the polymer composition of the present invention is preferably 1 to 200 parts by weight, more preferably 2 to 120 parts by weight, and still more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the polymer material. It is. By making content of a clay mineral into the said range, the barrier property with respect to the mechanical characteristic of the obtained crosslinked material and a molded object and gas and a liquid can be improved more.
  • the polymer composition of the present invention contains the above-described polymer material, a polyether compound having a cationic group, and a clay mineral.
  • the polymer composition of the present invention is prepared by mixing a polymer material, a polyether compound having a cationic group, and a clay mineral.
  • the clay mineral used in the present invention usually has a multilayer structure having exchangeable cations between layers.
  • the cationic property contained in the polyether compound having the cationic group is included.
  • the group acts on the multilayer structure through the exchangeable cation of the clay mineral to separate such multilayer structure and to interact with the separated multilayer structure, so that the clay mineral becomes organic. Become.
  • the clay mineral thus organized interacts with a polyether compound having a cationic group, it becomes lipophilic by the action of the main chain of the polyether compound having a cationic group. It will also have.
  • the clay mineral is made organic by the action of the polyether compound having such a cationic group, and further made oleophilic so that the multilayer structure is separated. Can be dispersed well in the polymer material, and the resulting cross-linked product and molded product have excellent mechanical properties, while being separated into a gas or liquid by the separated multilayer structure. On the other hand, it can also have excellent barrier properties.
  • the polyether compound having a cationic group used in the present invention is to make the clay mineral organic by interacting with the clay mineral by a positive charge contained in the cationic group.
  • the site interacting with the clay mineral by the electric charge of the structure becomes a structure covered with the main chain structure of the polyether compound.
  • the part that interacted with the clay mineral by the positive charge is covered with the main chain structure of the polyether compound, so that the clay mineral can be oleophilic, and as a result, the clay mineral is polymerized. It can be dispersed well in the material.
  • the organized clay mineral cannot be dispersed well in the polymer material, so the effect of blending the clay mineral is not effective. It cannot be obtained sufficiently.
  • the occurrence of such defects can be effectively suppressed, and the clay mineral is excellent in the polymer material in a mode in which the multilayer structure is separated. In this way, the resulting cross-linked product and molded product have excellent mechanical properties, and an excellent barrier against gas and liquid due to the separated multilayer structure. It can also have property.
  • the technical scope of the present invention is not limited to the above consideration.
  • the polymer composition of the present invention may be prepared by mixing a polymer material, a polyether compound having a cationic group, and a clay mineral, and the mixing order thereof is not particularly limited.
  • the polymer material, the polyether compound having a cationic group, and a clay mineral may be mixed at the same time, or the polymer material and the polyether compound having a cationic group may be mixed in advance.
  • a method may be used in which a clay mineral is mixed and further mixed.
  • a polyether compound having a cationic group and a clay mineral may be mixed in advance, and a polymer material may be blended therein and further mixed, or the polymer material and the clay mineral may be mixed in advance.
  • the method of mixing the polymer material, the polyether compound having a cationic group, and the clay mineral is not particularly limited, but any mixer such as a kneader, a banbury, a brabender, an open roll, a calender roll, a twin screw extruder, or the like. And a method of mixing by using one or a plurality of them in combination.
  • a shear force is applied and shear mixing is performed to obtain a polymer composition. It is preferable to obtain a product, whereby the clay mineral can be dispersed in a state where the multilayer structure is further separated, and the barrier property against gas and liquid of the resulting crosslinked product and molded product can be further increased. it can.
  • the polymer composition of the present invention may contain other additives usually blended in the polymer material.
  • additives include, but are not limited to, fillers; acid acceptors; reinforcing agents; anti-aging agents; plasticizers; ultraviolet absorbers; light stabilizers; tackifiers; Examples include an imparting agent, an electrolyte substance, a colorant (dye / pigment), a flame retardant, and the like.
  • the crosslinkable composition of the present invention is a crosslinkable composition obtained by blending the above-described polymer composition of the present invention with a crosslinking agent.
  • the crosslinking agent may be any compound that can crosslink the polymer material, and may be appropriately selected according to the type of the crosslinkable group possessed by the polymer material to be used.
  • a sulfur-based crosslinking agent or an organic peroxide crosslinking agent can be used.
  • Sulfur-based crosslinking agents include powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, and other sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, N, Sulfur-containing compounds such as N′-dithio-bis (hexahydro-2H-azepinone-2), phosphorus-containing polysulfides, polymer polysulfides; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4′-morpholinodithio) And sulfur donating compounds such as 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 content of the crosslinking agent in the crosslinkable composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polymer material. It is.
  • crosslinking accelerator when sulfur or a sulfur-containing compound is used as the crosslinking agent, it is preferable to use a crosslinking accelerator and a crosslinking accelerator in combination.
  • the crosslinking acceleration aid is not particularly limited, and examples thereof include zinc oxide and stearic acid.
  • a crosslinking accelerator For example, a guanidine type compound; an aldehyde-amine type compound; an aldehyde-ammonia type compound; a thiazole type compound; a sulfenamide type compound; a thiourea type compound; a thiuram type compound; Salt-based compounds; and the like can be used.
  • crosslinking assistant and the crosslinking accelerator one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of each of the crosslinking accelerator and the crosslinking accelerator is not particularly limited, but is preferably 0.01 to 15 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer material.
  • the crosslinked product of the present invention is obtained by crosslinking the above-described crosslinkable composition of the present invention.
  • the cross-linking method is not particularly limited, and may be selected according to the shape and size of the cross-linked product to be obtained.
  • a cross-linkable composition is formed using a uniaxial or multi-axial extruder. A method of extruding to form a molded body, followed by heating and crosslinking; injection molding machine, extrusion blow molding machine, transfer molding machine, press molding machine, etc. A method of crosslinking; and the like.
  • 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 2 hours.
  • the cross-linked product even if the surface is cross-linked, it may not be sufficiently cross-linked to the inside, so it may be further heated to carry out secondary cross-linking.
  • the molded article of the present invention is obtained by molding the above-described polymer composition of the present invention.
  • the molding method is not particularly limited, and may be selected according to the shape, size, etc. of the molded body to be obtained.
  • a composition for a molded body using a uniaxial or multiaxial extruder is used.
  • the molding temperature is usually 50 to 400 ° C, preferably 100 to 350 ° C.
  • the crosslinked product and molded product of the present invention are obtained using the above-described polymer composition of the present invention, they have excellent mechanical properties and have excellent barrier properties against gases and liquids. It is. Therefore, the cross-linked product and molded product of the present invention make use of such properties, and when the polymer material is a resin, various uses such as a case / panel, packaging film, optical lens, etc. for automobiles and electrical devices. Can be suitably used. Further, when the polymer material is rubber, it can be suitably used for various applications such as a sealing material, a gasket, a belt, or a hose, and can be particularly suitably used for a hose. For example, when the crosslinked product of the present invention is used for a hose having a multilayer structure, at least one layer of the multilayer structure constituting the hose may be formed of the crosslinked product of the present invention.
  • the structure of the polyether compound having a cationic group and the content of the oxirane monomer unit having the cationic group are determined using a nuclear magnetic resonance apparatus (NMR). The measurement was performed as follows. That is, first, 30 mg of a polyether compound having a cationic group as a sample was added to 1.0 mL of heavy dimethyl sulfoxide and shaken for 1 hour to be uniformly dissolved. Then, NMR measurement was performed on the obtained solution to obtain a 1 H-NMR spectrum, and the structure of the polyether compound having a cationic group was assigned according to a conventional method.
  • NMR nuclear magnetic resonance apparatus
  • Mooney viscosity The Mooney viscosity (ML1 + 4, 100 ° C) of the rubber was measured at 100 ° C according to JIS K6300.
  • the permeation amount of the solution every 24 hours was measured, and the maximum amount was defined as a fuel permeation coefficient (unit: g ⁇ mm / m 2 ⁇ day).
  • the measurement was performed for 14 days.
  • the fuel permeation coefficient was determined by an index with the result of Comparative Example 1 as 100. The smaller this value, the lower the fuel permeation coefficient and the better the fuel permeation resistance.
  • Oxygen permeability A test piece having a thickness of 100 ⁇ m was obtained by hot pressing the sheet-like resin-like molded body. The obtained test piece was subjected to oxygen permeation measuring device (product name “OX-TRAN 2 / 21MH”, manufactured by MOCON Co., Ltd.) under the conditions of 23 ° C. and 0% relative humidity in accordance with JIS K7126-2. ) was used to measure the oxygen transmission rate per 1 m 2 of the test piece (cc / m 2 ⁇ day ⁇ atm). The oxygen transmission rate was determined by an index with the result of Comparative Example 2 as 100. The smaller this value, the lower the oxygen transmission rate and the better the gas barrier property.
  • the obtained polymerization reaction liquid was diluted with toluene and then poured into 2-propanol to obtain a white rubbery substance with a yield of 11.9 g.
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • the composition ratio of each element was in good agreement with the composition ratio predicted from the structure. From the above, it was identified as a cationic group-containing polyether compound A having a 1-methylimidazolium chloride group and a polymerization degree of 110.
  • Reaction was performed. Thereafter, when the polymerization conversion rate with respect to all charged monomers reached 75% by weight, 0.3 part of hydroxylamine sulfate and 0.2 part of potassium hydroxide were added to stop the polymerization reaction. After stopping the reaction, the contents in the reaction vessel were heated to 70 ° C., and unreacted monomers were recovered by steam distillation under reduced pressure to obtain a latex of nitrile rubber B (solid content: 24% by weight). And about the obtained latex of the nitrile rubber B, solid nitrile rubber B was obtained by performing coagulation
  • the content ratio of each monomer constituting the monomer of the obtained nitrile rubber B was measured by H 1 -NMR using an FT-NMR apparatus (trade name: JNM-EX400WB, manufactured by JEOL Ltd.). However, it was 50% by weight of acrylonitrile monomer unit, 48% by weight of 1,3-butadiene monomer unit, and 2% by weight of 2-vinylpyridine monomer unit.
  • the Mooney viscosity [ML1 + 4 (100 ° C.)] of the obtained nitrile rubber B was 85.
  • the Mooney viscosity [ML1 + 4 (100 ° C.)] of the obtained nitrile rubber C was 78.
  • Example 1 100 parts of nitrile rubber B obtained in Production Example 3, 15 parts of purified bentonite (trade name “Bengel HVP”, manufactured by Hojun Co., clay mineral), and cationic group-containing polyether compound A 1 obtained in Production Example 2 .5 parts was charged into a plastic coder lab station (W50EHT) manufactured by Brabender, which was heated to 110 ° C., and shear mixing was performed at a rotation speed of 50 rpm for 5 minutes to obtain a rubber-like polymer composition.
  • W50EHT plastic coder lab station
  • the resulting crosslinkable composition was hot pressed at 160 ° C. for 20 minutes to form and crosslink, thereby obtaining a sheet-like rubber cross-linked product having a thickness of 2 mm.
  • measurement of 100% tensile stress and evaluation of fuel permeability were performed. The results are shown in Table 1.
  • Example 2 A polymer composition, a crosslinkable composition, and a sheet-like rubber cross-linked product are obtained in the same manner as in Example 1 except that the amount of the cationic group-containing polyether compound A is changed from 1.5 parts to 5 parts. The same evaluation was performed. The results are shown in Table 1.
  • Example 3 The polymer was changed in the same manner as in Example 1 except that the amount of the cationic group-containing polyether compound A was changed from 1.5 parts to 5 parts and the amount of purified bentonite was changed from 15 parts to 30 parts. A composition, a crosslinkable composition, and a sheet-like rubber cross-linked product were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 4 Instead of 100 parts of the nitrile rubber B obtained in Production Example 3, 100 parts of the nitrile rubber C obtained in Production Example 4 was used, and the amount of the cationic group-containing polyether compound A was used from 1.5 parts. Except having changed to 5 parts, it carried out similarly to Example 1, and obtained the polymer composition, the crosslinkable composition, and the sheet-like rubber crosslinked material, and evaluated similarly. The results are shown in Table 1.
  • Example 1 A polymer composition, a crosslinkable composition, and a sheet-like rubber cross-linked product were obtained in the same manner as in Example 1 except that the cationic group-containing polyether compound A was not blended, and evaluation was performed in the same manner. The results are shown in Table 1.
  • TEM-35B product name “TEM-35B”
  • Example 2 A polymer composition and a sheet-like resin-like molded product were obtained in the same manner as in Example 5 except that the cationic group-containing polyether compound A was not blended, and evaluation was performed in the same manner. The results are shown in Table 2.
  • Example 5 As shown in Table 2, a resin-like molded product (Example 5) obtained by using a polymer composition containing a cycloolefin polymer as a polymer material, a polyether compound having a cationic group, and a clay mineral was a cation. Compared with the case where the polyether compound having a functional group is not contained (Comparative Example 2), the flexural modulus is high, the mechanical properties are excellent, the oxygen permeability is low, and the gas barrier properties are excellent.

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Abstract

L'invention concerne : une composition polymère contenant un matériau polymère, un composé de polyéther contenant un groupe cationique et un minéral argileux ; ainsi qu'un produit réticulé et un corps moulé, chacun étant obtenu au moyen de cette composition polymère.
PCT/JP2018/005112 2017-02-15 2018-02-14 Composition de polymère, produit réticulé et corps moulé obtenus au moyen de cette composition WO2018151163A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155520A (ja) * 2007-12-27 2009-07-16 Kao Corp アレルゲン不活化剤
WO2011001657A1 (fr) * 2009-07-01 2011-01-06 独立行政法人科学技術振興機構 Dendrimère polyionique et hydrogel comprenant celui-ci
JP2013227432A (ja) * 2012-04-26 2013-11-07 Nippon Zeon Co Ltd ゴム架橋物および導電性部材
JP2014224194A (ja) * 2013-05-16 2014-12-04 日産化学工業株式会社 カチオン型水溶性高分子およびそれよりなるハイドロゲル
JP2016192502A (ja) * 2015-03-31 2016-11-10 日本ゼオン株式会社 色素増感太陽電池素子
WO2017170367A1 (fr) * 2016-03-31 2017-10-05 日本ゼオン株式会社 Composition polymère à base de polyéther

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155520A (ja) * 2007-12-27 2009-07-16 Kao Corp アレルゲン不活化剤
WO2011001657A1 (fr) * 2009-07-01 2011-01-06 独立行政法人科学技術振興機構 Dendrimère polyionique et hydrogel comprenant celui-ci
JP2013227432A (ja) * 2012-04-26 2013-11-07 Nippon Zeon Co Ltd ゴム架橋物および導電性部材
JP2014224194A (ja) * 2013-05-16 2014-12-04 日産化学工業株式会社 カチオン型水溶性高分子およびそれよりなるハイドロゲル
JP2016192502A (ja) * 2015-03-31 2016-11-10 日本ゼオン株式会社 色素増感太陽電池素子
WO2017170367A1 (fr) * 2016-03-31 2017-10-05 日本ゼオン株式会社 Composition polymère à base de polyéther

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