WO2010101106A1 - Composition de caoutchouc dans laquelle de multiples sortes de groupes de réticulation peuvent être formées - Google Patents

Composition de caoutchouc dans laquelle de multiples sortes de groupes de réticulation peuvent être formées Download PDF

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WO2010101106A1
WO2010101106A1 PCT/JP2010/053216 JP2010053216W WO2010101106A1 WO 2010101106 A1 WO2010101106 A1 WO 2010101106A1 JP 2010053216 W JP2010053216 W JP 2010053216W WO 2010101106 A1 WO2010101106 A1 WO 2010101106A1
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group
polymer
rubber
hydrogen
rubber composition
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PCT/JP2010/053216
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Japanese (ja)
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知野　圭介
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横浜ゴム株式会社
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Priority claimed from JP2009050345A external-priority patent/JP2010202784A/ja
Priority claimed from JP2009094509A external-priority patent/JP4957745B2/ja
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Publication of WO2010101106A1 publication Critical patent/WO2010101106A1/fr

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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to a rubber composition that can form two or more crosslinkable groups. More specifically, the present invention relates to a rubber composition capable of forming two or more types of crosslinkable groups, a hydrogen bond crosslinkable group and a covalent bond crosslinkable group.
  • Patent Document 1 describing the invention relating to the applicant's application includes a side chain containing a hydrogen-bonded cross-linking site having a carbonyl-containing group and a nitrogen-containing heterocycle, and the other side containing a covalent-bonded cross-linking site. It consists of an elastomeric polymer having a chain and a glass transition point Tg of 25 ° C.
  • the main chain of the elastomeric polymer is composed of diene rubber, olefin rubber, or (hydrogenated) polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester or polyamide elastomeric polymer.
  • An elastomeric polymer having a cyclic acid anhydride group in the side chain A nitrogen-containing heterocycle obtained by reacting with a part of the cyclic acid anhydride group of the above and a carbonyl-containing group derived from the cyclic acid anhydride group opened by the reaction is a hydrogen-bonding cross-linking site
  • a thermoplastic elastomer in which an unreacted cyclic acid anhydride group becomes a covalently linked cross-linking site is disclosed, and this thermoplastic elastomer retains excellent recyclability and has excellent mechanical strength. It is stated.
  • An object of the present invention is a rubber composition capable of forming two or more types of crosslinkable groups, a hydrogen bond crosslinkable group and a covalent bond crosslinkable group, wherein the covalent bond crosslinkable group is converted to an organic peroxide crosslinker and a sulfur-added group.
  • An object of the present invention is to provide a thermosetting rubber composition capable of forming a thermosetting rubber crosslinked with at least one kind of sulfur.
  • the object of the present invention is to provide a polymer (a) alone or a blend of the polymer (a) and a diene rubber (b) in which a hydrogen bonding group is formed in a polymer molecule, with an organic peroxide and sulfur.
  • the rubber composition is a polymer obtained by sequentially reacting a carbonyl group-containing unsaturated compound and a nitrogen-containing heterocyclic compound containing a functional group capable of reacting with the carbonyl group in the polymer main chain. Achieved by:
  • the crosslinked rubber obtained by subjecting the rubber composition according to the present invention to organic peroxide crosslinking and / or sulfur vulcanization has two or three types of crosslinking groups, hydrogen bonding crosslinking group and covalent bonding crosslinking group. Because it is cross-linked, it has higher modulus, breaking strength and tear strength than those of hydrogen bond crosslinkable group alone or covalent bond crosslinkable group alone, and higher elongation at break than those of covalent bond crosslinkable alone, The compression set characteristics are equivalent.
  • the cross-linked blend rubber obtained by vulcanization is composed of a cross-linked rubber (A) blended with a cross-linked diene rubber (B) and two types of hydrogen bond cross-linkable groups and covalent bond cross-linkable groups (covalent cross-links are peroxides).
  • Cross-linked or sulfur vulcanized or three types (covalent cross-links are peroxide cross-linked and sulfur vulcanized) cross-linkable groups, so that the cross-linked rubber (A) is a hydrogen bond cross-linkable group alone or a covalent bond
  • the modulus and breaking strength are higher than those of the bond-crosslinkable group alone, the elongation at break is higher than that of the bond-crosslinkable group alone, and the compression set properties are equivalent.
  • Such characteristics include tight organic peroxide cross-linking and / or sulfur vulcanization combined with slow hydrogen-bond cross-linking, resulting in increased stress and reduced stress concentration, elongation, tensile strength, This is probably because the tear strength has increased.
  • the crosslinked rubber of the present invention having such properties is effectively used for applications such as pneumatic tires and hoses.
  • Examples of the polymer that forms a hydrogen bonding group include polyolefin polymers; diene rubbers; rubbers having unsaturated carbon atoms in the main chain; non-diene rubbers such as rubbers having atoms other than carbon atoms in the main chain; A plastic elastomer or the like is used.
  • ethylene / propylene copolymer rubber EPM
  • EPDM ethylene / propylene / diene copolymer rubber
  • elastomers that can be the main chain of the polymer include diene rubbers; polyolefin rubbers, rubbers having unsaturated carbon bonds in the main chain [for example, butyl rubber (IIR)], and rubbers having atoms other than carbon atoms in the main chain.
  • IIR butyl rubber
  • Non-diene rubbers such as these; thermoplastic elastomers (TPE) and the like.
  • diene rubber as an elastomer that can be a main chain of the polymer
  • examples of the diene rubber as an elastomer that can be a main chain of the polymer include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), Examples include acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), and hydrogenated products thereof.
  • NR natural rubber
  • IR isoprene rubber
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • CR chloroprene rubber
  • the polyolefin rubber as an elastomer that can be a main chain of the polymer is not particularly limited as long as it has a polymethylene type saturated main chain.
  • hydrocarbons such as complete hydrogenated products of ethylene-propylene rubber (EPM), ethylene-octene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-butene rubber (EBM), polyethylene rubber, polypropylene rubber, diene rubber
  • EVA ethylene-vinyl alcohol rubber
  • CM chlorinated polyethylene
  • CSM chlorosulfonated polyethylene
  • FKM fluoro rubber
  • ACM acrylic rubber
  • AEM ethylene-acrylic rubber
  • examples thereof include polyolefin rubber having such a functional group.
  • Non-diene rubber as an elastomer that can be the main chain of the polymer includes, for example, a rubber having an unsaturated carbon bond in the main chain such as butyl rubber, or epichlorohydrin rubber (CO, ECO), polysulfide rubber, silicone rubber, Non-diene rubbers having atoms other than carbon atoms in the main chain, such as urethane rubber.
  • a rubber having an unsaturated carbon bond in the main chain such as butyl rubber, or epichlorohydrin rubber (CO, ECO), polysulfide rubber, silicone rubber, Non-diene rubbers having atoms other than carbon atoms in the main chain, such as urethane rubber.
  • thermoplastic elastomer examples include, for example, styrene-based TPE (for example, SBS, SIS, SEBS, SEPS, or hydrogenated products thereof), olefin-based TPE, and diene-based TPE (for example, 1 2-BR, trans IR type), vinyl chloride type TPE, urethane type TPE, ester type TPE, amide type TPE, fluorine type TPE, and the like.
  • the main chain of the polymer is preferably a polyolefin-based rubber from the viewpoint that the obtained crosslinked rubber composition has excellent tensile strength and can suppress deterioration of the composition because there is no double bond. More preferred are polyolefin-based rubbers consisting of only ethylene-propylene rubber (EPM) and ethylene-octene rubber.
  • EPM ethylene-propylene rubber
  • the ethylene content is from the viewpoint of excellent compression set resistance and mechanical strength of the resulting crosslinked rubber composition, the content is preferably 10 to 90 mol%, more preferably 40 to 90 mol%.
  • the soot polymer may be liquid or solid.
  • the molecular weight of the polymer is not particularly limited, and can be appropriately selected according to the use in which the rubber composition of the present invention is used, the physical properties required for these, and the like. From the viewpoint of excellent strength of the crosslinked rubber composition of the present invention, the polymer is preferably solid at room temperature, and when the polymer main chain that is solid at room temperature is a polyolefin-based rubber, its weight average molecular weight Mw is It is preferably 100,000 or more, particularly preferably about 150,000 to 1,500,000.
  • the weight average molecular weight Mw is a weight average molecular weight Mw (polystyrene conversion) measured by gel permeation chromatography (GPC). For the measurement, tetrahydrofuran (THF) is preferably used as a solvent.
  • the main chain is composed of a polyolefin polymer molecule, and the polymer main chain is obtained by sequentially reacting with a carbonyl group-containing unsaturated compound and a nitrogen-containing heterocyclic compound containing a functional group capable of reacting with the carbonyl group.
  • the polyolefin polymer molecule is subjected to an addition reaction with a carbonyl group-containing unsaturated compound such as maleic anhydride and maleic acid, preferably maleic anhydride.
  • the addition reaction of maleic anhydride is carried out under reaction conditions such as the presence of an organic peroxide, but in practice, commercially available products can be used as they are.
  • the reaction is carried out by an ene reaction without using an organic peroxide.
  • the modification rate of maleic anhydride is generally set to about 0.1 to 10% by weight based on the weight of the polyolefin polymer molecule to be modified.
  • commercially available products or modified products thereof may be used as the polymer in which hydrogen bonding groups are formed and its precursor.
  • examples of commercially available products include maleic anhydride-modified isoprene rubber such as LIR-403 (Kuraray product) and LIR-410A (Kuraray prototype); modified isoprene rubber such as LIR-410 (Kuraray product); Clinac 110, 221; Carboxy-modified nitrile rubber such as 231 (Polycer product); Carboxy-modified polybutene such as CPIB (Nisseki Chemical Lab), HRPIB (Nisseki Chemical Lab prototype); Nukurel (Mitsui DuPont polychemical product), Yucaron (Mitsubishi Chemical product) , Maleic anhydride modified ethylene-propylene rubber such as Tuffmer M (for example, MA8510 (Mitsui Chemicals)); maleic anhydride modified ethylene-butene rubber such as Tuffmer M (for example, MH7020 (Mitsui Chemicals)
  • Examples of the side chain containing a nitrogen-containing heterocyclic ring and a carbonyl group in one side chain include those containing a structure represented by the following formula (1).
  • A is a nitrogen-containing heterocyclic ring
  • B is a linking group, and a single bond, an oxygen atom, a sulfur atom, an amino group NR ′ and an organic group which may contain an oxygen atom, a sulfur atom or an amino group NR ′
  • R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the polymer has a side chain in which at least part or all of the side chains contain a carbonyl group and a nitrogen-containing heterocycle in one side chain ( It preferably has a structure represented by 1).
  • the nitrogen-containing heterocycle A is not particularly limited as long as it contains a nitrogen atom in the heterocycle, and can have a heteroatom other than the nitrogen atom, for example, a sulfur atom, an oxygen atom, a phosphorus atom, etc. in the heterocycle. .
  • the nitrogen-containing heterocyclic ring A may have a substituent.
  • substituents include alkyl groups such as methyl group, ethyl group, (iso) propyl group, and hexyl group; alkoxy groups such as methoxy group, ethoxy group, and (iso) propoxy group; fluorine atom, chlorine atom, bromine atom or A group consisting of a halogen atom which is an iodine atom; a cyano group; an amino group; an aromatic hydrocarbon group; an ester group; an ether group; an acyl group;
  • the substituents can be used alone or in combination of two or more, and the number thereof is not limited.
  • the nitrogen-containing heterocyclic ring A can have aromaticity.
  • the nitrogen-containing heterocyclic ring A has aromaticity, it is preferable because the crosslinked rubber composition obtained by crosslinking the composition by hydrogen bonding or the like is excellent in tensile strength, mechanical strength, and the like.
  • the nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring.
  • nitrogen-containing heterocycle examples include pyrrolidine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, ⁇ -isoindigo, monoporphyrin, Diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyloerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone , Pyrazolidone, indazole, pyridoindole,
  • the bonding position of the nitrogen-containing heterocycle will be described.
  • the nitrogen-containing heterocycle is referred to as “nitrogen-containing n-membered ring compound (n ⁇ 3)”.
  • the binding positions described below (“1 to n-position”) are based on the IUPAC nomenclature.
  • the bonding position is determined by the order based on the IUPAC nomenclature. Specifically, the bonding positions are indicated on the 5-membered, 6-membered and condensed nitrogen-containing heterocycles exemplified below.
  • the bonding position of the nitrogen-containing n-membered ring compound is not particularly limited, and any bonding position (position 1 to position n) ) Preferably, it is the 1-position or 3-position to n-position.
  • the nitrogen-containing n-membered ring compound contains one nitrogen atom (for example, a pyridine ring), the chelate is easily formed in the molecule, and the physical properties such as the tensile strength when the composition is used are excellent.
  • the (n-1) position is preferred.
  • the nitrogen-containing five-membered ring includes the following group of compounds, a triazole derivative represented by the following formula (2), and an imidazole derivative represented by the following formula (3). preferable.
  • the substituent X is not particularly limited as long as the substituent is an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • substituent X examples include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, and a stearyl group; an isopropyl group, an isobutyl group, an s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 2-ethylhexyl group and other branched alkyl groups; benzyl group, phenethyl group and other aralkyl groups; phenyl And aryl groups such as a tolyl group (o-, m-, p-), a dimethylphenyl group, and a mesityl group.
  • a linear alkyl group such as a
  • nitrogen-containing six-membered ring examples include the following group of compounds and isocyanuric acid (for example, trimers of isocyanate group-containing compounds).
  • the nitrogen-containing six-membered ring may have the above-described substituent, or may have a hydrogen atom added or eliminated.
  • the nitrogen-containing heterocycle may be a condensed ring having a nitrogen-containing heterocycle, and examples thereof include those condensed with a benzene ring and those condensed with nitrogen-containing heterocycles. Specific examples include the following group of condensed rings.
  • the condensed ring may have the above-described substituent, or may have a hydrogen atom added or eliminated.
  • Examples of isocyanuric acid include those represented by the following formula.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom; an alkyl group such as a methyl group or an ethyl group; an alkoxyl group such as a methoxy group or an ethoxy group; a hydroxyl group such as a hydroxymethyl group or a hydroxyethyl group A group-containing group; a halogen atom such as a chlorine atom or a bromine atom; a hydroxyl group; a cyano group; an amino group; an ester group; R 1, R 2, R 3 may be different from each may be the same.
  • Examples of isocyanuric acid include 1,3,5-tris (2-hydroxyethyl) isocyanuric acid.
  • the obtained crosslinked rubber composition is excellent in compression set resistance, mechanical strength and hardness, from the viewpoint of triazole ring, thiadiazole ring, pyridine ring, thiazole ring, imidazole ring, hydantoin ring, Isocyanuric acid is preferred.
  • the nitrogen-containing heterocyclic ring-containing groups can be used alone or in combination of two or more.
  • the bonding group B is at least one selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, an amino group NR ′ and an organic group which may contain an oxygen atom, a sulfur atom or an amino group NR ′, and R ′ is a hydrogen atom. It is preferably an atom or an alkyl group having 1 to 10 carbon atoms.
  • This organic group is a hydrocarbon group that can contain an oxygen atom, a sulfur atom or an amino group NR ′, and examples of the hydrocarbon group include an alkylene group having 1 to 20 carbon atoms (for example, —CH 2 CH 2 —). Is mentioned.
  • the organic group has at least one selected from the group consisting of an oxygen atom, a sulfur atom and an amino group NR ′ at the terminal or side chain, for example, an alkylene ether group having 1 to 20 carbon atoms (an alkyleneoxy group such as -O-CH 2 CH 2 -) , alkyleneamino group (e.g. -NH-CH 2 CH 2 -) , alkylene thioether group (alkylene thio group, for example, -S-CH 2 CH 2 -) and the like.
  • an alkylene ether group having 1 to 20 carbon atoms an alkyleneoxy group such as -O-CH 2 CH 2 -
  • alkyleneamino group e.g. -NH-CH 2 CH 2 -
  • alkylene thioether group alkylene thio group, for example, -S-CH 2 CH 2 -
  • R 'in the amino group NR' is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group And includes isomers.
  • the bonding group B which is at least one selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, an amino group NR ′ and an organic group which may contain an oxygen atom, a sulfur atom or an amino group NR ′ is a mechanical group. From the viewpoint of excellent strength, it is preferable to form an ester group, an amide group, an imide group, a thioester group or the like adjacent to the carbonyl group in the formula (1).
  • the linking group B may contain an oxygen atom, a sulfur atom, an amino group NR ′, an oxygen atom, a sulfur atom or an amino group NR ′ that forms a conjugated system adjacent to the carbonyl group in the formula (1).
  • alkylene ether group having 1 to 20 carbon atoms, an alkyleneamino group or an alkylenethioether group having at least one selected from the group consisting of organic groups, and an amino group (NH), alkyleneamino group (—NH -CH 2 -, - NH-CH 2 CH 2 -, - NH-CH 2 CH 2 CH 2 -), alkylene ether group (-O-CH 2 -, - O-CH 2 CH 2 -, - O-CH 2 CH 2 CH 2- ) is more preferable.
  • Each of the bonding groups B can be used alone or in combination of two or more.
  • Examples of the side chain containing the structure represented by the formula (1) include structures represented by the following formulas (5) and (6).
  • A is a nitrogen-containing heterocyclic ring
  • B and D are each independently an organic group that may contain a single bond, an oxygen atom, a sulfur atom, an amino group NR ′, and an oxygen atom, a sulfur atom, or an amino group NR ′.
  • R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is directly or via an organic group in the ⁇ -position or ⁇ -position to the main chain of the polymer. Join.
  • the nitrogen-containing heterocycle A is basically the same as the nitrogen-containing heterocycle A of the formula (1).
  • the linking groups B and D are basically the same as the linking group B in the formula (1).
  • the substituent D in the formula (5) is a C 1-20 alkylene group which may contain a single bond, an oxygen atom, a sulfur atom or an amino group NR ′ from the viewpoint of excellent compression set and mechanical strength.
  • an aralkylene group in which an oxygen atom, a sulfur atom, or an amino group NR ′ forms a conjugated system with an imide nitrogen is preferable, and a single bond is more preferable.
  • the substituents D can be used alone or in combination of two or more.
  • the reaction of a nitrogen-containing heterocyclic compound substituted with a functional group having reactivity with maleic anhydride or the like is performed at about 170 in a kneader in the absence of a reaction solvent, as shown in Examples of Patent Document 1.
  • the reaction can be carried out under reaction conditions such as kneading at ⁇ 200 ° C. for 30 minutes, but it can also be carried out by using a reaction solvent such as chloroform and reacting at room temperature or higher for several minutes to about 1 hour.
  • the functional group of the nitrogen-containing heterocyclic compound that reacts with maleic anhydride or the like is used in an equivalent amount or more, and as shown in the following reaction formula, first, an amic bond in which an amide bond is formed with one carboxyl group. Although an acid is formed, an imide bond is formed as the dehydration reaction further proceeds.
  • a donor-H- as represented by OH ... O, NH ... O, OH ... N, NH ... N Hydrogen bonds consisting of acceptors are formed there, allowing self-crosslinking.
  • the hydrogen-bonding polyolefin polymer thus obtained is peroxide-crosslinked or sulfur vulcanized with an organic peroxide such as dicumyl peroxide, and the polyolefin-based polymers are covalently crosslinked.
  • These hydrogen bondable polymers have a peroxide crosslinkable or sulfur vulcanizable diene rubber content of 0 to 99 wt%, preferably 1 to 1 wt%, preferably 99 to 15 wt%. It can be blended at a ratio of 85% by weight.
  • Peroxide crosslinking is applicable to all diene rubbers other than butyl rubber
  • sulfur vulcanization is applicable to all diene rubbers: natural rubber, polyisoprene, emulsion polymerization SBR, solution polymerization SBR, high cis butadiene rubber, butyl rubber. Etc. are applicable.
  • diene rubbers are polymer (a) precursors that are polymers before forming hydrogen bonds of the hydrogen-bonding polymer, for example, polymers having hydrogen-bonding groups formed in the polymer molecule in the polymer main chain.
  • a polymer obtained by sequentially reacting a carbonyl group-containing unsaturated compound and a nitrogen-containing heterocyclic compound containing a functional group capable of reacting with the carbonyl group the polymer reacted with the carbonyl group-containing unsaturated compound After blending, a reaction is performed to form hydrogen bonds in the hydrogen bonding polymer.
  • Arbitrary organic peroxides are used as the organic peroxide used for the peroxide crosslinking of the diene rubber (b) blended to the hydrogen bonding polymer (a) and the diene rubber (b) blended therewith.
  • organic peroxides are 0.1 to 5 mol%, preferably 0.3 to 0.3 mol%, together with hydrogen-bond crosslinkable groups formed in an amount of 0.1 to 10 mol%, preferably 0.3 to 5 mol%, based on the monomer polymerization unit of the polymer main chain. It is used in such a ratio as to form ⁇ 3 mol% covalently crosslinkable group. More specifically, it is used at a ratio of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight per 100 parts by weight of the blend rubber.
  • a vulcanization accelerator in combination with the hydrogen-bonding polymer (a) to achieve covalent crosslinking and further to vulcanize the sulfur of the diene rubber (b) blended therein.
  • Accelerators include thiazole (MBT, MBTS, ZnMBT, etc.), sulfenamide (CBS, DCBS, BBS, etc.), guanidine (DPG, DOTG, OTBG, etc.), thiuram (TMTD, TMTM, TBzTD, TETD, TBTD, etc.), dithiocarbamate (ZTC, NaBDC, etc.), xanthate (ZnBX, etc.), etc. are used.
  • sulfur vulcanization systems are used in an amount of 0.1 to 5 mol%, preferably 0.1 to 0.1 mol%, preferably 0.1 to 5 mol%, and 0.1 to 5 mol% of hydrogen-bonding crosslinkable groups formed with respect to the monomer polymer units in the polymer main chain. It is used in such a ratio as to form ⁇ 3 mol% covalently crosslinkable group.
  • sulfur is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.4 to 0.8 parts by weight
  • vulcanization accelerator is 0.1 to 10 parts by weight per 100 parts by weight of the blend rubber. Parts, preferably 0.1 to 5 parts by weight, particularly preferably 2 to 5 parts by weight, and the vulcanization accelerator is used in a weight ratio of 2.5 to 12 with respect to sulfur.
  • the rubber composition containing the above-mentioned components as essential components further includes a compounding agent generally used as a compounding agent for rubber, for example, a reinforcing agent or filler such as carbon black, silica, talc, graphite, calcium silicate, etc.
  • a processing aid such as stearic acid, an acid acceptor such as zinc oxide, a softener, a plasticizer, an anti-aging agent and the like are appropriately blended and used as necessary.
  • Preparation of the composition is carried out by kneading by a general method using a kneader or mixer such as a kneader or Banbury mixer and an open roll, etc., and mixing of the organic peroxide or sulfur and the vulcanization accelerator is open. Done by roll.
  • the obtained rubber composition is subjected to a crosslinking temperature or sulfur vulcanization temperature corresponding to the decomposition temperature of the organic peroxide used, for example, at about 150 to 200 ° C. for about 1 to 30 minutes, and peroxide crosslinking is performed there.
  • a covalently crosslinkable group consisting of a functional group or a sulfur crosslinkable group is formed.
  • maleinized EPM Hereinafter abbreviated as “maleinized EPM”
  • maleinized EPM 3-amino-1,2,4-triazole
  • Nippon Carbite ATA Nippon Carbite ATA
  • a nitrogen-containing heterocycle is introduced into the modified EPM, and after further kneading for 5 minutes, 1.0 part by weight of an anti-aging agent (Sumitomo Chemical product Antigen 6C) is added, and the mixture is further kneaded for 3 minutes and released.
  • an anti-aging agent Suditomo Chemical product Antigen 6C
  • this kneaded product was reintroduced into a pressure kneader heated to 100 ° C., and after kneading for 3 minutes, 1 part by weight of dicumyl peroxide (NOF product Park Mill D) was added, and further for 1 minute 30 seconds After kneading, it is discharged.
  • the resulting composition was press-molded at 180 ° C. for 15 minutes in various test piece molds, and the test pieces (hydrogen bond crosslinkable group and covalent bond crosslinkable group (organic peroxide crosslink)) were used.
  • Cross-linked EPM cross-linked product was prepared and various measurements were performed.
  • Example 2 At the time of preparing the composition of Example 1, the amount of dicumyl peroxide (Park Mill D) was changed to 1.5 parts by weight, and similarly crosslinked by press molding (covalently crosslinked by hydrogen bond crosslinking groups and organic peroxide crosslinking). EPM cross-linked with two cross-linkable groups) and measurements were performed.
  • Park Mill D dicumyl peroxide
  • Comparative Example 1 At the time of preparing the composition of Example 1, dicumyl peroxide was not used, and the composition was prepared with 1.29 parts by weight of 3-amino-1,2,4-triazole and 1.0 part by weight of an antioxidant (antigen 6C). Similarly, cross-linking (hydrogen bond cross-linked EPM cross-linked product) and measurement were performed by press molding.
  • Example 2 100 parts by weight of maleated EPM not reacted with 4H-3-amino-1,2,4-triazole was used, 1.0 part by weight of dicumyl peroxide (Parkmill D) and an anti-aging agent (antigen 6C). A composition was prepared together with 1.0 part by weight, and similarly crosslinked (covalently crosslinked EPM crosslinked product) and measurement were performed by press molding.
  • Example 2 100 parts by weight of maleated EPM not reacting with 4H-3-amino-1,2,4-triazole was used, 1.5 parts by weight of dicumyl peroxide (Parkmill D) and an antioxidant (antigen 6C) A composition was prepared together with 1.0 part by weight, and similarly crosslinked (covalently crosslinked EPM crosslinked product) and measurement were performed by press molding.
  • JIS A Conforms to JIS K6253 corresponding to ASTM D1415 (measured for a 12.5 cm thick Rupke test sample)
  • Tensile properties JIS K6251 compliant with ASTM D412 No. 3 dumbbell specimen is punched from a 2mm thick sheet at 25 ° C , Tensile test at 500mm / min, 100% modulus (M100), Measures 200% modulus (M200), 300% modulus (M300), breaking strength and elongation at break Compression permanent set: Conforms to JIS K6262 corresponding to ASTM D395 (25% compression, 70 ° C, 22 time) Tear strength: JIS K6252 compliant with ASTM D624
  • Example 3 and Comparative Examples 4 to 5 In each of the above examples and comparative examples, a maleated natural rubber (1.5% by mole of hydrogen bonding group, 2.17% by weight of maleating) was used instead of maleated EPM. The amount of each component of the composition used (unit: parts by weight) and the measurement results are shown in Table 2 below.
  • Example 4 100 parts by weight of the maleated EPM 4H-3-amino-1,2,4-triazole (ATA) 1.29 Anti-aging agent (Antigen 6C) 1.0 ⁇ Zinc Hana (Zonhua Chemical Product Zinc Hua 3) 3.0 ⁇ Stearic acid (NOF product beads stearic acid) 2.0 ⁇ Sulfur (Sulfur processed oil from Karuizawa Refinery) 0.6 ⁇ Vulcanization accelerator (Sanshin Chemical Product Sunseller CM-PO) 3.0 ⁇ A composition comprising the above components is vulcanized at 160 ° C. for 15 minutes, and crosslinked with two types of crosslinkable groups: hydrogen bondable crosslinkable groups and covalently crosslinkable groups obtained by sulfur vulcanization. Got.
  • ATA Maleated EPM 4H-3-amino-1,2,4-triazole
  • Antigen 6C 1.0 ⁇ Zinc Hana (Zonhua Chemical Product Zinc Hua 3) 3.0 ⁇ Stearic acid (NOF product
  • Example 5 In Example 4, the same amount (100 parts by weight) of maleated EPDM (maleinization ratio: 1.5% by weight) was used in place of maleated EPM, and hydrogen bonded crosslinkable groups and covalently crosslinkable groups by sulfur vulcanization were used. An EPDM cross-linked product cross-linked with two cross-linkable groups was obtained.
  • maleated EPDM maleinization ratio: 1.5% by weight
  • Example 4 Comparative Example 6 In Example 4, the same amount (100 parts by weight) of EPM (Mitsui Chemicals Tuffmer P-0775) was used instead of maleated EPM, and 4H-3-amino-1,2,4-triazole (ATA) was used. In addition, a crosslinked EPM crosslinked product by sulfur vulcanization was obtained.
  • EPM Mitsubishi Chemicals Tuffmer P-0775
  • ATA 4H-3-amino-1,2,4-triazole
  • Example 7 Comparative Example 7 In Example 4, the same amount (100 parts by weight) of EPDM (Mitsui Chemicals product ENB-EPDM3085) was used instead of maleated EPM, and 4H-3-amino-1,2,4-triazole (ATA) was not used. In addition, a crosslinked crosslinked EPDM product by sulfur vulcanization was obtained.
  • EPDM Mitsubishi Chemicals product ENB-EPDM3085
  • ATA 4H-3-amino-1,2,4-triazole
  • Example 8 Comparative Example 8 In Example 4, a zinc bond, stearic acid, sulfur and a vulcanization accelerator (Sunceller CM-PO) were not used, and a hydrogen bond crosslinked EPDM crosslinked product crosslinked with a hydrogen bond crosslinking group was obtained.
  • maleated EPM 25 parts by weight of natural rubber (P0215) and 4 minutes of mastication, 4H-3-amino-1,2,4-triazole (Nippon Carbite)
  • product ATA 0.32 parts by weight of product ATA
  • anti-aging agent Suditomo Chemical product Antigen 6C
  • this kneaded product was reintroduced into a pressure kneader heated to 100 ° C., and after kneading for 3 minutes, 1.5 parts by weight of dicumyl peroxide (NOF product Park Mill D) was added, and further for 1 minute 30 seconds After kneading, it is discharged.
  • the resulting composition was press-molded at 180 ° C. for 15 minutes in various test piece molds, and the test pieces (hydrogen bond crosslinkable group and covalent bond crosslinkable group (organic peroxide crosslink)) were used.
  • a cross-linked EPM cross-linked product and a natural rubber organic peroxide cross-linked product) were prepared, and various measurements were performed.
  • Example 7 In Example 6, the amount of maleated EPM was changed to 50 parts by weight, the amount of natural rubber was changed to 50 parts by weight, and the amount of 4H-3-amino-1,2,4-triazole was changed to 0.64 parts by weight.
  • Example 8 In Example 6, the amount of maleated EPM was changed to 75 parts by weight, the amount of natural rubber was changed to 25 parts by weight, and the amount of 4H-3-amino-1,2,4-triazole was changed to 0.96 parts by weight.
  • Examples 9 to 11 and Comparative Example 10 In Examples 6 to 8 and Comparative Example 9, EPDM (Sumitomo Chemical Products Esprene 505) was used in the same amount instead of natural rubber.
  • Comparative Example 15 In Comparative Example 12, natural rubber was not used, and the EPM amount was changed to 100 parts by weight.
  • test pieces obtained in Examples 6 to 11 and Comparative Examples 9 to 18 were measured for tensile properties and compression set.
  • Example 12 In Example 7, the same amount (50 parts by weight) of maleated natural rubber (hydrogen bond group 1.5 mol%, maleated rate 2.17 wt%) was used instead of natural rubber, and 4H-3-amino-1,2, The amount of 4-triazole was changed to 1.29 parts by weight. The reaction with 4H-3-amino-1,2,4-triazole was carried out on a blend of maleated EPM and maleated natural rubber.
  • Example 12 The measurement results in Example 12 and Comparative Example 19 are shown in Table 6 below.
  • Table 6 Measurement Example 12 Comparative Example 19
  • Example 13 Maleated EPM 25 parts by weight SBR (Nippon ZEON product Nipol 1502) 75 ⁇ 4H-3-Amino-1,2,4-triazole 0.32 ⁇ Anti-aging agent (Antigen 6C) 1.0 ⁇ Zinc Hana (Zonhua Chemical Product Zinc Hua 3) 3.0 ⁇ Stearic acid (NOF product beads stearic acid) 2.0 ⁇ Sulfur (Sulfur processed oil from Karuizawa Refinery) 0.6 ⁇ Vulcanization accelerator (Sanshin Chemical Product Sunseller CM-PO) 3.0 ⁇ A composition comprising the above components is vulcanized at 160 ° C. for 15 minutes, and crosslinked with two types of crosslinkable groups: hydrogen bondable crosslinkable groups and covalently crosslinkable groups obtained by sulfur vulcanization. A blend of SBR with sulfur vulcanization was obtained.
  • Example 14 In Example 13, the amount of maleated EPM was changed to 50 parts by weight, the amount of SBR was changed to 50 parts by weight, and the amount of 4H-3-amino-1,2,4-triazole was changed to 0.64 parts by weight.
  • Example 15 In Example 13, the amount of maleated EPM was changed to 75 parts by weight, the amount of SBR was changed to 25 parts by weight, and the amount of 4H-3-amino-1,2,4-triazole was changed to 0.96 parts by weight.
  • Examples 6 to 8 have higher modulus and breaking strength than Comparative Example 9 of natural rubber alone, and higher modulus than Comparative Examples 12 to 14 in which EPM was used instead of maleated EPM. .
  • Examples 7 to 8 have higher breaking strength than Comparative Example 11 with maleated EPM alone, and higher breaking strength than Comparative Examples 13 to 14.
  • Examples 9-11 are higher in modulus and breaking strength than Comparative Example 10 with EPDM alone, and in Comparative Examples 12-18 where EPDM is used instead of natural rubber. The modulus is high.
  • Example 11 has higher breaking strength than Comparative Example 11 with maleated EPM alone.
  • Example 12 has higher modulus and higher fracture strength and better compression set than Comparative Example 19 in which 4H-3-amino-1,2,4-triazole was not used.
  • Examples 13 to 15 have higher modulus or breaking strength than Comparative Example 20 with SBR alone, higher breaking strength than Comparative Example 21 with maleated EPM alone, good compression set, and The modulus and breaking strength are higher than those of Comparative Examples 22 to 24 in which neither maleated EPM nor 4H-3-amino-1,2,4-triazole was used.
  • Examples 14 to 15 have a higher modulus than Comparative Example 21 with maleated EPM alone.

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Abstract

L'invention porte sur une composition de caoutchouc préparée par incorporation d'un peroxyde organique et/ou de soufre soit dans un polymère (a) qui présente, dans la molécule, des groupes capables de former des liaisons hydrogène, soit dans un mélange du polymère (a) avec un caoutchouc diénique (b), deux ou trois sortes de groupes de réticulation, y compris des groupes de réticulation de type par liaisons hydrogène, (qui peuvent former des réticulations de type par liaisons hydrogène), pouvant être formées dans le polymère (a). Dans la composition de caoutchouc, de multiples sortes de groupes de réticulation peuvent être formées, lesdites multiples sortes de groupes de réticulation comprenant à la fois des groupes de réticulation de type par liaisons hydrogène et de groupes de réticulation de type par liaisons covalentes. Ainsi, la composition de caoutchouc peut fournir un caoutchouc thermodurci qui a été réticulé soit par réaction de réticulation des groupes de réticulation de type par liaisons covalentes avec le peroxyde organique et/ou par une réaction de vulcanisation de celle-ci par le soufre.
PCT/JP2010/053216 2009-03-04 2010-03-01 Composition de caoutchouc dans laquelle de multiples sortes de groupes de réticulation peuvent être formées WO2010101106A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009050345A JP2010202784A (ja) 2009-03-04 2009-03-04 ２種以上の架橋性基を形成し得るゴム組成物
JP2009-050345 2009-03-04
JP2009094509A JP4957745B2 (ja) 2009-04-09 2009-04-09 ２種以上の架橋基を形成し得るポリマーを含有するブレンドゴム組成物
JP2009-094509 2009-04-09

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002080529A (ja) * 2000-06-29 2002-03-19 Yokohama Rubber Co Ltd:The 熱可塑性ポリマー
JP2005068210A (ja) * 2003-08-28 2005-03-17 Yokohama Rubber Co Ltd:The 熱可塑性エラストマー組成物
JP2005306948A (ja) * 2004-04-20 2005-11-04 Jsr Corp 熱可塑性エラストマー組成物の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002080529A (ja) * 2000-06-29 2002-03-19 Yokohama Rubber Co Ltd:The 熱可塑性ポリマー
JP2005068210A (ja) * 2003-08-28 2005-03-17 Yokohama Rubber Co Ltd:The 熱可塑性エラストマー組成物
JP2005306948A (ja) * 2004-04-20 2005-11-04 Jsr Corp 熱可塑性エラストマー組成物の製造方法

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