[go: up one dir, main page]

WO2003070797A1 - Caoutchouc dienique conjugue, caoutchouc etendu a l'huile et composition de caoutchouc - Google Patents

Caoutchouc dienique conjugue, caoutchouc etendu a l'huile et composition de caoutchouc Download PDF

Info

Publication number
WO2003070797A1
WO2003070797A1 PCT/JP2003/001795 JP0301795W WO03070797A1 WO 2003070797 A1 WO2003070797 A1 WO 2003070797A1 JP 0301795 W JP0301795 W JP 0301795W WO 03070797 A1 WO03070797 A1 WO 03070797A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
monomer
weight
polymerization
conjugated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2003/001795
Other languages
English (en)
Japanese (ja)
Inventor
Takeshi Karato
Yoshihiro Chino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Publication of WO2003070797A1 publication Critical patent/WO2003070797A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • 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

Definitions

  • the present invention relates to a conjugated rubber, an oil-extended rubber and a rubber composition. More specifically, a conjugated gen-based rubber which is excellent in the surface shape of a sheet when a compound containing silica as a reinforcing agent is formed into a sheet by a roll, and which is excellent in tensile properties and low heat generation,
  • the present invention relates to an oil-extended rubber containing an extension oil, and a rubber composition containing the rubber.
  • JP-A-64-222940 discloses a conjugated gen-based rubber obtained by copolymerizing an amino group-containing monomer by solution polymerization using an organic alkali metal or the like as a polymerization catalyst.
  • Silica-containing rubber compositions with improved breaking strength and abrasion resistance have been disclosed.
  • This publication also discloses a specific compounding example in which a styrene-butadiene copolymer rubber having a natural rubber rubber viscosity of about 50 is blended with the conjugated gen-based rubber.
  • Japanese Patent Application Laid-Open No. 1-101344 discloses that a tertiary amino group-containing monomer containing a conjugated gen-based rubber obtained by emulsifying and copolymerizing 1 to 20% by weight of a tertiary amino group is obtained.
  • a silica-containing rubber composition having excellent properties and the like is disclosed.
  • This publication also discloses a specific example of blending a styrene-butadiene copolymer rubber having a natural rubber rubber viscosity of about 50 with this conjugated diene rubber.
  • rubber compositions containing such conjugated rubbers are inferior in processability, and the rubber blends exemplified above are insufficient in processability, and have a balance between low heat build-up and tensile properties. However, it is hard to say that it is good.
  • Japanese Patent Application Laid-Open No. 8-134272 discloses a conjugated rubber containing a tertiary amino group-containing monomer of less than 1% by weight and a silane coupling agent.
  • a silica compounded rubber composition kneaded under conditions is disclosed.
  • Such a rubber composition has excellent extrudability and excellent tensile properties and low heat build-up, but the surface shape of the rubber composition when formed into a sheet by a roll is not satisfactory. Did not. Disclosure of the invention
  • an object of the present invention is to provide an excellent sheet surface shape when a compound containing silica as a reinforcing agent is formed into a sheet by a roll, and to have tensile properties and low heat build-up. It is an object of the present invention to provide a conjugated gen-based rubber excellent in water resistance, an oil-extended rubber obtained by blending the rubber with an extension oil, and a rubber composition containing the rubber.
  • the present inventors have conducted intensive studies in order to achieve the above object, and have found that when copolymerizing 1,3-butylene, styrene and an amino group-containing monomer, 1,3-butadiene and After the polymerization of styrene is started, the polymerization can be obtained by adding an amino group-containing monomer and a molecular weight modifier in a state where a polymer having a relatively high Mooney viscosity is present in the reaction system.
  • a conjugated rubber comprising 20% by weight and having a viscosity (Ml) of 20 to 150, wherein at least a part of a conjugated monomer used for polymerization and an aromatic vinyl Contains at least a part of the monomer, does not contain a polar group-containing monomer, or
  • the polymerization of the monomer mixture containing less than 30% by weight is started, and the addition of the remaining conjugated diene monomer and the remaining aromatic vinyl monomer is completed by the time the polymerization is stopped.
  • the remainder of the group-containing monomer and the molecular weight modifier are combined with the viscosity of the polymer in the reaction system.
  • (M 2) is in the range of 70 to 200, and is added while it is higher than M 1 by 5 or more. . Further, according to the present invention, there is provided an oil-extended rubber comprising the conjugated rubber and an extending oil.
  • the conjugated diene rubber of the present invention has a conjugated diene monomer unit of 40 to 99.9% by weight, an aromatic vinyl monomer unit of 0 to 59.9% by weight, and a polar group-containing monomer unit of 0. It is a conjugated rubber composed of 1 to 20% by weight and having a Mooney viscosity (Ml) of 20 to 150, and is a rubber obtained by a specific polymerization method. That is, at the time of producing the syngeneic rubber of the present invention, at least a part of the conjugated gen monomer used for the polymerization is contained, and when an aromatic vinyl monomer is used, at least a part thereof is used.
  • the polymerization is started by using a monomer mixture containing no polar group-containing monomer or containing less than 30% by weight of the monomer as the initially charged monomer mixture. Thereafter, the addition of the remaining conjugated diene monomer and the remaining aromatic vinyl monomer is completed by the time the polymerization is stopped. Further, the remaining monomer of the polar group-containing monomer and the molecular weight modifier are mixed with each other in such a manner that the Mooney viscosity (M 2) of the polymer in the reaction system is in the range of 70 to 200, and The polymerization is continued by adding while the viscosity is at least 5 times higher than the conjugated rubber's viscosity (Ml).
  • M 2 Mooney viscosity
  • the conjugated diene rubber is composed of 40 to 99.9% by weight, preferably 50 to 89.8% by weight, more preferably 55 to 9.7% by weight, conjugated diene monomer unit, and aromatic vinyl monomer unit.
  • An aromatic vinyl monomer unit is preferably included because it contributes to improvement in tensile properties. However, if the amount is excessive, the tensile properties are inferior.
  • the amount of the polar group-containing monomer unit is small, low heat build-up and tensile properties are inferior.
  • the amount is large, the surface shape of the silica-containing rubber composition formed into a sheet by a roll becomes poor. If the Mooney viscosity is low, low heat build-up and tensile properties are inferior.On the contrary, if it is high, the surface shape of the silica-containing rubber composition molded into a sheet with a roll deteriorates, or the viscosity of the compound becomes too high to process. It will be difficult.
  • the conjugated diene rubber contains other monomer units other than the conjugated diene monomer unit, the aromatic vinyl monomer unit and the polar group-containing monomer unit within a range that does not essentially impair the effects of the present invention. May be included.
  • the amount is preferably at most 20% by weight, more preferably at most 10% by weight. If the amount is too large, the physical balance of the crosslinked rubber tends to deteriorate.
  • conjugated diene monomer examples include 1,3-butadiene, 2-methyl-3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene. Is mentioned. Of these, 1,3-butadiene is preferred. These can be used alone or in combination of two or more.
  • aromatic vinyl monomer an aromatic vinyl compound having no polar group is used.
  • examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, and 4-t-butylstyrene. , 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monoflurostyrene, and the like. Of these, styrene is preferred. These can be used alone or in combination of two or more.
  • the polar group-containing monomer is a polymerizable monomer having at least one polar group in one molecule.
  • the polar group is not particularly limited as long as it can react with the silica surface. Examples thereof include an amino group, an epoxy group, an alkoxysilyl group, an aryloxyxyl group, a hydroxyl group, a sulfido group, and a disulfide. Group, a sulfonyl group, a sulfinyl group, a thiol group, an imino group, and an imide group.
  • an amino group, an epoxy group, an alkoxysilyl group, an aryloxyl silyl group, and a hydroxyl group are preferred, an amino group, an epoxy group, an alkoxysilyl group, and an aryloxyl silyl group are more preferred, and the epoxy group and the amino group are more preferred.
  • the amino group-containing monomer is a polymerizable monomer having at least one amino group selected from primary, secondary and tertiary amino groups in one molecule, and among them, tertiary amino group Are preferred.
  • Examples of the primary amino group-containing monomer include P-aminostyrene, aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, aminobutyl acrylate, aminomethyl methacrylate, aminoethyl methacrylate, and aminopropyl. Methacrylate, aminobutyl methacrylate, and the like.
  • Examples of the secondary amino group-containing monomer include anilinostyrenes disclosed in JP-A-61-135355; N-methylacrylamide, N-ethylacrylamide, and N-methylmetha.
  • N-monosubstituted acrylamides and N-monosubstituted methacrylamides such as acrylamide, N-ethylmethacrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide, and the like.
  • tertiary amino group-containing monomers include, for example, N, N-disubstituted aminoalkyl Crylate, N, N-disubstituted aminoalkyl acrylamide, N, N-disubstituted aminoalkyl methacrylate, N, N-disubstituted aminoalkyl methacrylamide, N, N-disubstituted aminoalkyl aromatic vinyl compound and pyridyl group And the like.
  • N, N-disubstituted aminoalkyl (meth) acrylate examples include N, N-dimethylaminomethyl (meth) acrylate, N, N—dimethylaminoethyl (meth) acrylate, N, N— Dimethylaminopropyl (meth) acrylate, N, N—Dimethylaminobutyl (meth) acrylate, N, N—Jethylaminoethyl (meth) acrylate, N, N—Jetylaminopropyl ) Acrylate, N, N—Jethylaminobutyl (meth) acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate, N, N—Dipropylaminoethyl (meth) acrylate, N, N-dibutylamino Ethyl (meth) acrylate, N, N-dibutylaminopropyl (me
  • N, N-dimethylaminoethyl (meth) acrylate, N, N-getylaminoethyl (meth) acrylate and N, N-dipropylaminoethyl (meth) acrylate are preferred.
  • N, N-disubstituted aminoalkyl (meth) acrylamide examples include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylamino Propyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-Diethylaminoethyl (meth) acrylamide, N, N—Getylaminopropyl
  • N, N-disubstituted aminoalkyl aromatic vinyl compound examples include N, N-dimethylaminoethylstyrene, N, N-dimethylethylethylstyrene, N, N-dipropylaminoethylstyrene, N, N— And diethyl octylaminoethylstyrene.
  • Examples of the polymerizable monomer having a pyridyl group include 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine and the like. Among these, 2-vinylpyridine and 4-vinylpyridine are preferred.
  • amino group-containing monomers can be used alone or in combination of two or more.
  • the epoxy group-containing monomer is a polymerizable monomer having at least one epoxy group in one molecule.
  • Epoxy group-containing monomers include, for example, glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4 xycyclohexyl acrylate, N-glycidyl acrylamide, glycidyl methacrylate, 3,4-epoxy heptyl Methacrylate, 3,4-year-old xycyclohexyl methacrylate, N-glycidyl methacrylamide, vinyldaricidyl ether, arylglycidyl ether, 2-methylarylglycidyl ether, 3,4-epoxy-1-butene 1,3-epoxy-1-methyl-1—butene, 3,4-epoxy— ⁇ —pentene, 3,4-epoxy—3—methyl-1-pentene, 5,6—epoxy—1-hexene And vinylcyclohexene monooxide, styrene-p-glycidyl ether and the like. Of these
  • the alkoxysilyl group-containing monomer is a polymerizable monomer having at least one alkoxysilyl group in one molecule.
  • alkoxysilyl group-containing monomer examples include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, / 3- (meth) acryloxyshethyltrimethoxysilane, 8) (Meth) acryloxysilyl triethoxysilane, ⁇ (meth) acryloxypropyl trimethoxysilane, ⁇ (meth) acryloxypropyl triethoxysilane, ⁇ (meth) acryl Roxypropyltripropoxysilane, ⁇ - (meth) acryloxypropyltributoxysilane, T- (meth) acryloxypropylmethyldimethoxysilane, r- (meth) acryloxypropylethyldimethoxysilane, r ⁇ (Meth) acryloxypropylhexyldimethoxysilane, / 3-acryloxyshethyl Trimethylene Bok
  • ⁇ chromatography ( ⁇ over methacryloxypropyl O carboxymethyl) propyl Bok Increment Bok Kishishiran the like.
  • alkoxysilyl group-containing monomers can be used alone or in combination of two or more.
  • the aryl-containing xylyl group-containing monomer is a polymerizable monomer having at least one aryl-containing xylyl group in one molecule.
  • aryl-containing xylsilyl group-containing monomer examples include, for example, (meth) acryloxymethyl triphenyl,) 8- (meth) acryloxyshethyl triphenyl, ⁇ - (meth) acryloxypropyl triphenyl Enoxysilane, acryl (meth) acryloxypropylmethyldiphenoxysilane, acryl (meth) acryloxypropylethyldiphenoxysilane, acryl (meth) acryloxypropylhexyldiphen Noxylsilane, jS-acryloxyshethyl xymethyltriphenoxysilane, ⁇ - () 8-acryloxyshethyloxy) propyl Trifrhenoxysilane, ⁇ — (T-methacryloxypropyl propyl) propyl Triphenyloxysilane and the like can be mentioned. Of these, preferred are (meth) acryloxypropyltriphenoxysilane and
  • aryl-containing xylsilyl group-containing monomers can be used alone or in combination of two or more.
  • the hydroxyl group-containing monomer is a polymerizable monomer having at least one primary, secondary or tertiary hydroxyl group in one molecule.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate.
  • hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-phenoxy-12-hydroxypropyl acrylate, glycerol monoacrylate, hydroxybutyl Acrylate, hydroxyhexyl acrylate, hydroxy octyl acrylate, 2-hydroxy Cypropylacrylamide, 3-hydroxypropylacrylamide, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-phenoxy-12-hydroxypropyl methacrylate, glycerol Monomethacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate, hydroxyoctyl methacrylate, 2-hydroxypropyl methacrylamide, 3-hydroxypropyl methacrylamide and the like are preferred.
  • the other monomer other than the conjugated gen, the aromatic vinyl monomer and the polar group-containing monomer is not particularly limited as long as it can be copolymerized with the conjugated gen or the like.
  • the conjugated rubber of the present invention In the production of the conjugated rubber of the present invention, at least a part of the conjugated monomer used for the polymerization is contained, and when an aromatic vinyl monomer is used, at least a part thereof is contained.
  • the polymerization is started by using a monomer mixture containing no polar group-containing monomer or containing less than 30% by weight thereof as the initially charged monomer mixture. Thereafter, the addition of the remainder of the conjugated diene monomer and the remainder of the aromatic vinyl monomer is completed by the time the polymerization is stopped.
  • the remainder of the polar group-containing monomer and the molecular weight modifier are mixed with each other when the Mooney viscosity (M 2) of the polymer in the reaction system is in the range of 70 to 200, and Continue the polymerization by adding while the viscosity is higher than 5 times the rubber viscosity (Ml) of the rubber.
  • the monomer composition used for the polymerization may be appropriately determined so that the composition of the conjugated rubber is within a predetermined range.
  • the monomer mixture contains at least a part of the conjugated gen monomer used in the polymerization, and further contains at least a part of the aromatic vinyl monomer when the aromatic vinyl monomer is used. It is essential that no polar group-containing monomer be contained or less than 30% by weight thereof.
  • the amount of the conjugated diene monomer used at the start of the polymerization is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably the total amount of the conjugated dimer used in the polymerization. is there.
  • the amount used at the start of the polymerization is preferably at least 80% by weight, more preferably at least 90% by weight, based on the amount of the aromatic vinyl monomer used in the polymerization. Particularly preferred is the total amount.
  • the amount of the polar group-containing monomer used at the start of the polymerization is preferably less than 25% by weight, more preferably less than 23% by weight, particularly preferably 0% by weight of the polar group-containing monomer used for the polymerization. Or less than 20% by weight.
  • the surface shape of the silica-containing rubber composition molded into a sheet with a roll may deteriorate.
  • the viscosity of the compound tends to be too high.
  • the amount of the polar group-containing monomer in the monomer mixture at the start of polymerization is large, the surface shape of the silica-containing rubber composition formed into a sheet by a roll is deteriorated, and the viscosity of the compound is reduced. It becomes too high and difficult to process.
  • the conjugated diene monomer and the aromatic vinyl monomer in the monomer mixture at the start of the polymerization is not the total amount of the conjugated diene monomer and the aromatic vinyl monomer used in the polymerization, the remaining The conjugated diene monomer and the aromatic vinyl monomer may be added to the polymerization reaction system before the termination of the polymerization.
  • the method of addition is not particularly limited, and a method of batch addition, divided addition, or continuous addition can be employed.
  • the timing of the addition is not particularly limited as long as it is before the termination of the polymerization, but it is preferable to add the polymer at a polymerization conversion of less than 65% by weight in the polymerization reaction system, and it is more preferable to add it at less than 60% by weight. It is good.
  • M2 at the time of addition preferably ranges from 80 to 150, more preferably from 90 to 140.
  • the Mooney viscosity of the polymer present in the polymerization reaction system is low, the low heat build-up and tensile properties are inferior, and if it is high, the surface shape of the silica-containing rubber composition molded into a sheet with rolls deteriorates. (4) The viscosity of the compound becomes too high, making processing difficult.
  • the molecular weight modifier is not added here, the final viscosity of the conjugated gen-based rubber increases, and the surface shape of the silica-containing rubber composition molded into a sheet with a roll deteriorates. Or the viscosity of the compound becomes too high, making processing difficult.
  • the amount of the molecular weight modifier added depends on the type of the molecular weight modifier, but M1 is in the range of 20 to 150 and the difference between M2 and M1 (M2-M1) is 5 or more. It is advisable to adjust as appropriate.
  • the timing of addition of the remainder of the polar group-containing monomer used in the polymerization and the molecular weight modifier is substantially the same, but the addition timing is shifted so long as the effects of the present invention are not essentially impaired. It may be added.
  • the addition method a method of adding all at once is preferable, but a method of adding in portions or adding continuously may be adopted.
  • M 1 is at least 5 lower than M 2
  • [ ⁇ 1 1 is more preferably 8-50 lower than 1 ⁇ 2
  • M 1 is 10-45 lower than M 2 Is particularly preferred. If this difference is small, the surface shape of the rubber compounded rubber composition formed into a sheet by a roll is deteriorated, and the viscosity of the compounded compound becomes too high, making processing difficult.
  • the amount of the polymer formed in the reaction system is preferably 20 to 80% by weight, more preferably 20 to 80% by weight of the total amount of the conjugated rubber obtained by polymerization. It is in the range from 30 to 75% by weight, particularly preferably from 40 to 70% by weight. When the amount of the produced polymer is in this range, the balance between the processability of the silica-containing rubber composition and the tensile properties and low heat build-up is excellent.
  • the polymerization method that can be employed in the present invention is not particularly limited, and examples thereof include an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method.
  • the emulsion polymerization method can be preferably employed because the heat of reaction during the polymerization reaction is easily removed and the productivity is excellent.
  • an ordinary emulsion polymerization method may be used.
  • a predetermined amount of the above-mentioned monomer is emulsified and dispersed in an aqueous medium in the presence of an emulsifier, and the emulsification polymerization is carried out with a polymerization initiator.
  • the amount of each monomer used is appropriately selected such that the amount of each monomer unit in the polymer becomes a desired content.
  • a long-chain fatty acid salt having 10 or more carbon atoms and a phosphate or rosinate are used.
  • Specific examples thereof include potassium sulfate and lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and other fatty acid salts or sodium salts.
  • the amount of the emulsifier to be used is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of all the monomers.
  • polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate; a combination of ammonium persulfate and ferric sulfate; a combination of an organic peroxide and ferric sulfate; And a redox initiator such as a combination of hydrogen peroxide and ferric sulfate;
  • the amount of the polymerization initiator to be used is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of all the monomers.
  • a molecular weight modifier is used to control the polymer viscosity.
  • the molecular weight regulator include mercaptans such as t-dodecylmercaptan and n-dodecylmercaptan, carbon tetrachloride, thiocyanic glycolic acid, diterpenes, tapino-lenes, and alterpinenes. .
  • mercaptans are preferred, and t-dodecyl mercaptan is more preferred, and can be used.
  • the amount of the molecular weight modifier to be used is not particularly limited, but is usually 0.01 to 5 parts by weight, preferably 0.02 to 1 part by weight, more preferably 100 parts by weight based on 100 parts by weight of all monomers. Is from 0.05 to 0.5 parts by weight.
  • the temperature of the emulsion polymerization can be appropriately selected depending on the type of the polymerization initiator to be used, but is usually 0 to 100, preferably 0 to 60 ° C.
  • the polymerization mode may be any of continuous polymerization, batch polymerization and the like.
  • the polymerization conversion at the time of stopping the polymerization reaction is preferably 85% by weight or less, more preferably 50 to 80% by weight, from the viewpoint of preventing gelation of the polymer. .
  • the polymerization reaction is stopped by adding a polymerization terminator to the polymerization system when a predetermined polymerization conversion rate is reached.
  • a polymerization terminator for example, Amine compounds such as tylhydroxylamine and hydroxylamine; quinone compounds such as hydroquinone and benzoquinone; sodium nitrite, sodium hydroxide, and the like.
  • an antioxidant may be added, if necessary.
  • salts such as sodium chloride, calcium chloride, and potassium chloride are used as the coagulant.
  • acids such as hydrochloric acid and sulfuric acid are added as necessary to adjust the pH of the coagulation system to a predetermined value.
  • the collected crumb is washed, dehydrated, and dried with a band drier to obtain a desired conjugated gen-based rubber. If desired, at the time of coagulation, a polymer latex and an extending oil that has been made into an emulsified dispersion can be mixed and recovered as an oil-extended rubber.
  • the conjugated gen-based rubber having M1 of 80 or more is preferably recovered as an oil-extended rubber because it has excellent dispersibility of the reinforcing agent and excellent balance of cross-linking properties.
  • the extender oil used for recovery as an oil extension rubber those commonly used in the rubber industry can be used, for example, paraffin extender oil, aromatic extender oil, naphthenic extender oil, etc. .
  • the pour point of the extender oil is preferably from 150 to 150 ° C, more preferably from -10 to 130 ° C. Within this range, it is easy to stretch and is excellent in balance between wear resistance and low heat generation.
  • the aroma carbon content (CA%) of the extended oil by Kurz analysis is preferably 2% or more, more preferably 20% or more, and the paraffin carbon content (CP%) is preferably 70% or less, More preferably, it is 55%. If the %% is too small or the CP% is too large, the tensile properties and wear resistance will be insufficient.
  • the polycyclic aromatic content of the extender oil is preferably less than 3%. This content is measured by the method of IP346 (the inspection method of THIINSTITUTTEPETOLEM in the UK).
  • the compounding amount of the extender oil is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight with respect to 100 parts by weight of the conjugated rubber. Parts.
  • the blending amount of the extender oil is within this range, the viscosity of the blended compound containing silica is appropriate, and the balance between the tensile properties and the low heat generation is excellent.
  • the rubber composition of the present invention contains the conjugated rubber or the oil-extended rubber comprising the conjugated rubber and an extension oil.
  • the rubber composition of the present invention preferably contains at least one selected from silica and carbon black as a reinforcing agent, and particularly preferably contains silica as an essential component.
  • a reinforcing agent a carbon-silica dual phase filler in which silica is supported on the surface of carbon black may be used.
  • silica examples include dry-type white carbon, wet-type white carbon, colloidal silica, and precipitated silica disclosed in JP-A-62-262838.
  • a wet-process white carbon containing hydrous carboxylic acid as a main component is particularly preferable.
  • These silicas can be used alone or in combination of two or more.
  • the specific surface area of silica is not particularly limited, it is preferably 50 to 400 mV g, more preferably 100 to 220 m 2 / g, and particularly preferably 120 to 400 in terms of nitrogen adsorption specific surface area (BET method). 1 90 m 2 / g. When the specific surface area of the silica is within this range, the balance between tensile properties and low heat build-up is excellent.
  • the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTMD303 7-81.
  • furnace black for example, furnace black, acetylene black, thermal black, channel black, graphite, and the like can be used.
  • furnace black is particularly preferable, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HA F— Grades such as LS and FEF.
  • SAF SAF
  • ISAF ISAF-HS
  • ISAF-LS ISAF-LS
  • IISAF-HS High Speed F-HS
  • HAF HAF-HS
  • HA F— Grades such as LS and FEF.
  • the specific surface area of carbon black is not particularly limited, a nitrogen absorption specific surface area (N 2 SA), preferably more preferably 5 ⁇ 20 Om ⁇ g 50 m ⁇ 1 50 m 2 / g, particularly preferably 80 to 130 m 2 / g.
  • N 2 SA nitrogen absorption specific surface area
  • the nitrogen adsorption specific surface area is in this range, the tensile properties are more excellent.
  • the DBP adsorption amount of bonbon black is also not particularly limited, but is preferably 5 to 300 mI / 100 g, more preferably 50 to 200 ml "100 g, and particularly preferably. Is 80 to 16 0171 110 g When the DBP adsorption amount is within this range, the tensile properties are more excellent.
  • the specific surface area of adsorption (CTAB) of cetyl trimethylammonium bromide disclosed in Japanese Patent Application Laid-Open No. Hei 5-23090 is 110 to 17 Om 2.
  • CAB adsorption
  • DBP 24 M4 DBP
  • the compounding amount of the reinforcing agent is preferably 100 to 200 parts by weight, more preferably 20 to 150 parts by weight, and particularly preferably 30 to 120 parts by weight, based on 100 parts by weight of the rubber component. Parts by weight.
  • the mixing ratio is preferably silica: carbon black by weight, preferably 10:90 to 99: 9.
  • silica is contained as a reinforcing agent in the rubber composition of the present invention, it is preferable to add a silane coupling agent for the purpose of further improving tensile properties and low heat build-up.
  • silane coupling agent examples include vinyltriethoxysilane, 8- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and N— (i8-aminoethyl) -1-aminopropyltrimethoxysilane. , Bis (3- (triethoxysilyl) propyl) tetrasulfide, bis (3- (triethoxysilyl) propyl) disulfide, etc., and those described in JP-A-6-248116.
  • Tetrasulfides such as trimethoxysilylpropyl dimethylthiocapillamyl trisulfide and ⁇ -trimethoxysilylpropyl benzothiazyl ditrasulfide. Since silane can be avoided during kneading, silane The coupling agent is preferably one having four or less sulfur contained in one molecule. These silane coupling agents can be used alone or in combination of two or more.
  • the amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 2 to 10 parts by weight, based on 100 parts by weight of silica. is there.
  • the rubber composition of the present invention may contain other rubbers other than the conjugated gen-based rubber of the present invention as long as the effects of the present invention are not substantially impaired.
  • Other rubbers include, for example, natural rubber, octacis-polyisoprene rubber, high-cis-polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, butyl rubber, ethylene-propylene-copolymer rubber, and the like.
  • the rubber composition of the present invention contains, in addition to the above components, compounding agents such as a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an antioxidant, an activator, a plasticizer, a lubricant, and a filler according to a conventional method. A necessary amount can be contained.
  • compounding agents such as a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an antioxidant, an activator, a plasticizer, a lubricant, and a filler according to a conventional method. A necessary amount can be contained.
  • crosslinking agent examples include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxy oxide; Organic peroxides such as one-year-old oxide; p-quinone-diamine, ⁇ , ⁇ '-dibenzoylquinone-dioxime and other quinone-diamine; triethylenetetramine; hexamethylenediamine; Organic polyamine compounds such as 4,4'-methylenebis-1-o-chloroaniline; alkylphenol resins having a methyl alcohol group; and the like. Of these, sulfur is preferred, and powdered sulfur is particularly preferred. These crosslinking agents are used alone or in combination of two or more. The amount of the crosslinking agent to be added is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.
  • Crosslinking accelerators include ⁇ -cyclohexyl-2-benzothiazolesulfenamide, ⁇ -t-butyl-2-benzothiazolesulfenamide, N-sulfuroxyethylene-12-benzothiazolsulfenamide, N —Alkoxyethylene-1-2-benzothiazolesulfenamide, ⁇ , ⁇ '-diisopropyl-12-benzonitchi Sulfenamide-based cross-linking accelerators such as azolesulfenamide; guanidine-based cross-linking accelerators such as diphenyldananidine, diorthotriguanidine, and o-tolylbiguanidine; Thiazole crosslinking accelerators such as 2-mercaptobenzothiazole, dibenzothiazyldisulfide, and 2-mercaptobenzothiazole zinc salt; thiurams such as tetramethylthiurammonosulfide and tetramethylthiuram disulfide;
  • crosslinking accelerators may be used alone or in combination of two or more, but those containing a sulfenamide-based crosslinking accelerator are preferred.
  • the compounding amount of the crosslinking accelerator is preferably from 0.3 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.
  • cross-linking activator for example, higher fatty acids such as stearic acid and zinc oxide can be used.
  • zinc oxide those having a high surface activity and a particle size of 5 tm or less are preferable.
  • Specific examples of particularly preferred zinc oxide have a particle size of 0.05 to 0.5.
  • Zinc oxide may be surface-treated with an amine-based dispersant or wetting agent.
  • These crosslinking activators can be used alone or in combination of two or more.
  • the mixing ratio of the crosslinking activator is appropriately selected depending on the type of the crosslinking activator.
  • the blending amount of the higher fatty acid is preferably from 0.3 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.
  • the amount of zinc oxide is preferably from 0.1 to 5 parts by weight, more preferably from 0.5 to 2 parts by weight, based on 100 parts by weight of the rubber component.
  • examples of the compounding agent include an activator such as diethylene glycol, polyethylene glycol and silicone oil; a filler such as calcium carbonate, talc, clay and aluminum hydroxide; and a wax.
  • the rubber composition containing a reinforcing agent can be obtained by kneading the components according to a conventional method. For example, after kneading a compounding agent excluding a crosslinking agent and a crosslinking accelerator, a reinforcing agent, and a rubber component, a crosslinking agent and a crosslinking accelerator are added to the kneaded product, followed by kneading to obtain a rubber composition.
  • the kneading temperature of the compounding agent excluding the crosslinking agent and the crosslinking accelerator, the reinforcing agent, and the rubber component is preferably 80 to 200 ° C, more preferably 100 to 190 ° C, and particularly preferably. It should be in the range of 140 to ⁇ 80 ° C.
  • the obtained kneaded product is cooled to preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and then kneaded with a crosslinking agent and a crosslinking accelerator.
  • the rubber composition containing a reinforcing agent can be obtained as a wet master batch rubber by mixing a reinforcing agent in a predetermined ratio in advance into the polymer latex before obtaining the solid rubber.
  • the rubber composition of the present invention is usually used after crosslinking.
  • the crosslinking method is not particularly limited, and may be selected according to the shape and size of the crosslinked product.
  • the crosslinkable rubber composition may be filled in a mold and heated to perform crosslinking at the same time as molding. Alternatively, the crosslinkable rubber composition molded in advance may be heated to perform crosslinking.
  • the crosslinking temperature and the crosslinking time are not particularly limited, and may be selected according to the shape and size of the crosslinked product.
  • the crosslinking temperature is preferably from 120 to 200 ° C, more preferably from 140 to 180 ° C.
  • the properties of the copolymer rubber, oil point rubber, rubber composition and crosslinked rubber were evaluated by the following methods.
  • Styrene unit content in the copolymer Measured according to JIS K 6383 (refractive index method).
  • Epoxy group-containing monomer unit in the copolymer Dissolve the copolymer in tetrahydrofuran and reprecipitate twice with a mixed solvent of methanol / acetone (1/1 volume ratio). The sample was purified and dried under vacuum to obtain a sample. Dissolve the sample in tetrahydrofuran and add an excess of 0.1 N hydrochloric acid-acetone solution (0.1 N hydrochloric acid aqueous solution.
  • Viscosity (ML 1 + 4 , ⁇ 00 ° C): Measured according to JISK630.
  • Tensile properties The stress at 300% elongation (MPa) was measured in accordance with JIS K6301. This property was expressed as an index (tensile property index) using the reference sample as 100. The larger the value, the better.
  • a pressure-resistant reactor equipped with a stirrer was charged with 200 parts of deionized water, 2 parts of rosin stone, 2.1 parts of fatty acid stone, a monomer having an initial charge composition shown in Table 1, and t-dodecyl mercaptan.
  • the reactor temperature was set to 8 ° C, 0.1 parts of diisopropylbenzene hydroperoxide as a polymerization initiator, 5 parts of a deionized aqueous solution in which 0.2 parts of sodium diformaldehyde's sulfoxylate was dissolved, and 5 parts of ethylenediaminetetraacetate.
  • the polar group-containing monomer and t-dodecylmercaptan were added to the polymerization reaction system at the ratio shown in the immediately following post-addition composition to carry out the polymerization reaction.
  • the reaction was stopped by adding getylhydroxylamine to 0.05 part with respect to 100 parts of the polymer. I let it.
  • N- (1,3-dimethylbutyl) is used as an antioxidant for 100 parts of the polymer. 0.2 parts of 1 N'-phenyl-p-phenylenediamine and 0.13 parts of 2,2,4-trimethyl-1,2-dihydroquinoline were added as an emulsified dispersion, and conjugated rubber A A polymer latex was obtained.
  • a polymer latex of conjugated gen-based rubber A 37.5 parts of Enernene 184 A (manufactured by Pretty Petroleum Co.) was used as an extension oil for 100 parts of all polymers by emulsification and dispersion. Added as a liquid. Thereafter, the polymer latex containing the extended oil was coagulated with sodium chloride while adjusting the pH to 3 to 5 with sulfuric acid to obtain a crumb-like solid. The crumb was dried with a hot air dryer at 80 ° C to obtain an oil-extended rubber. Table 1 shows the Mooney viscosity of the obtained oil-extended rubber.
  • the kneaded product obtained was mixed with 1.4 parts of sulfur and a crosslinking accelerator (a mixture of 1.8 parts of N-cyclohexyl-2-benzothiazylsulfenamide and 1.7 parts of diphenyldananidin) in 5 parts. After kneading with an open roll at 0 ° C, the mixture was taken out into a sheet. The workability was evaluated by observing the surface skin and edge portion of the above sheet. Table 1 shows the results.
  • the sheet containing the vulcanizing agent was press-crosslinked at 160 ° C for 30 minutes to prepare a test piece, and the physical properties of the crosslinked rubber were evaluated. The results are shown to the meeting. However, in the occlusion, the stress at 300% elongation and t an ⁇ 5 are expressed using Comparative Example 2 as a reference (index 100).
  • Example 1 Same as Example 1 except that the initial charge composition and post-addition composition shown above were changed, and the conditions for coagulating the polymer latex were adjusted to pH 7, and calcium chloride was used. A conjugated gen-based rubber, an oil-extended rubber, a rubber composition, and a cross-linked rubber were produced, and their properties were evaluated. Table 1 shows the results.
  • Table 1 shows the following.
  • the silica-containing rubber composition of Comparative Example 1 using the conjugated diene rubber F without using the polar group-containing monomer has excellent workability, but is inferior in tensile properties and low heat build-up.
  • the silica-containing rubber composition of Comparative Example 2 using the conjugated diene rubber G obtained by charging the entire amount of the polar group-containing monomer before the start of polymerization is superior to Comparative Example 1 in tensile properties and low heat build-up. However, processability is poor.
  • the silica-containing rubber composition of Comparative Example 3 using the conjugated diene rubber H out of the specified range is inferior in processability, and inferior in tensile properties and low heat build-up.
  • the silica-containing rubber compositions of Examples 1 to 5 using the conjugated gen-based rubbers A to E within the range specified in the present invention are excellent in processability, and have excellent tensile properties and Excellent low heat generation.
  • the conjugated rubber of the present invention is excellent in the surface shape of a sheet when a compound containing silica as a reinforcing agent is formed into a sheet by a roll, and is excellent in tensile properties and low heat generation.
  • the rubber composition containing the conjugated rubber of the present invention can be used in various applications that make use of its properties, for example, tire members such as treads, under treads, carcass, sidewalls, and bead portions; hoses, It can be used for window frames, belts, shoe soles, anti-vibration rubber, anti-vibration rubber, rubber parts for automobile parts, etc .; resin-reinforced rubber parts such as high-impact polystyrene and ABS resin. Above all, it is suitable as a tire member and particularly suitable as a tire tread for a fuel-efficient tire.

Landscapes

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

Abstract

La présente invention concerne un caoutchouc diénique conjugué qui comprend 40 à 99,9 % en poids d'unités d'un monomère diénique conjugué, 0 à 59,9 % en poids d'unités d'un monomère de vinyle aromatique, et 0,1 à 20 % en poids d'unités d'un monomère polaire, ledit caoutchouc ayant une viscosité Mooney (M1) de 20 à 150 et étant produit au cours des étapes suivantes: initiation de la polymérisation d'un mélange monomérique comprenant au moins en partie le monomère diénique conjugué à polymériser et au moins en partie le monomère de vinyle aromatique à polymériser, et contenant le monomère polaire à polymériser en une quantité allant de 0 à moins de 30 % en poids; adjonction des restes de monomère diénique conjugué et de monomère de vinyle aromatique au système; et poursuite de la polymérisation avec adjonction simultanée du reste de monomère polaire et d'un agent de modification de poids moléculaire au système réactionnel jusqu'à ce que la viscosité Mooney du polymère dans le système prennent une valeur comprise dans l'intervalle 70 à 200 et supérieure à M1 d'au moins cinq. Ce caoutchouc a une excellente aptitude au traitement et peut servir à la fabrication d'articles en caoutchouc réticulé qui ont d'excellentes propriétés de résistance à la traction et sont peu sujets l'échauffement.
PCT/JP2003/001795 2002-02-20 2003-02-19 Caoutchouc dienique conjugue, caoutchouc etendu a l'huile et composition de caoutchouc Ceased WO2003070797A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-43994 2002-02-20
JP2002043994A JP3904063B2 (ja) 2002-02-20 2002-02-20 共役ジエン系ゴム、油展ゴムおよびゴム組成物

Publications (1)

Publication Number Publication Date
WO2003070797A1 true WO2003070797A1 (fr) 2003-08-28

Family

ID=27750539

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/001795 Ceased WO2003070797A1 (fr) 2002-02-20 2003-02-19 Caoutchouc dienique conjugue, caoutchouc etendu a l'huile et composition de caoutchouc

Country Status (2)

Country Link
JP (1) JP3904063B2 (fr)
WO (1) WO2003070797A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4615874B2 (ja) * 2004-02-02 2011-01-19 株式会社ブリヂストン ゴム組成物、これを用いたタイヤ及びゴム組成物の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04240297A (ja) * 1991-01-17 1992-08-27 Asahi Chem Ind Co Ltd 紙塗工用共重合体ラテックスの製造方法
JPH05170804A (ja) * 1991-12-24 1993-07-09 Mitsui Toatsu Chem Inc 共重合体ラテックスの製造方法及びその利用
JPH09183820A (ja) * 1995-12-29 1997-07-15 Nippon Zeon Co Ltd ジエン系ゴム及びその製造方法
JPH09208933A (ja) * 1996-01-29 1997-08-12 Fujimi Inkooporeetetsudo:Kk 研磨用組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3449724B2 (ja) * 1995-03-29 2003-09-22 日本ゼオン株式会社 ジエン系ゴム組成物
JP3656670B2 (ja) * 1996-01-31 2005-06-08 日本ゼオン株式会社 ゴム組成物
JP2002145965A (ja) * 2000-08-30 2002-05-22 Jsr Corp 共役ジエン系ゴム及び油展ゴム並びにこれらを含むゴム組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04240297A (ja) * 1991-01-17 1992-08-27 Asahi Chem Ind Co Ltd 紙塗工用共重合体ラテックスの製造方法
JPH05170804A (ja) * 1991-12-24 1993-07-09 Mitsui Toatsu Chem Inc 共重合体ラテックスの製造方法及びその利用
JPH09183820A (ja) * 1995-12-29 1997-07-15 Nippon Zeon Co Ltd ジエン系ゴム及びその製造方法
JPH09208933A (ja) * 1996-01-29 1997-08-12 Fujimi Inkooporeetetsudo:Kk 研磨用組成物

Also Published As

Publication number Publication date
JP3904063B2 (ja) 2007-04-11
JP2003238604A (ja) 2003-08-27

Similar Documents

Publication Publication Date Title
JP7751611B2 (ja) ゴム組成物
US11034821B2 (en) Rubber compositions
US11590799B2 (en) Heavy-duty tire rubber compositions and tires
JP2002338744A (ja) 油展ゴムおよびゴム組成物
EP3677637B1 (fr) Composition de caoutchouc pour pneumatique
US20200332090A1 (en) Heavy-duty tire rubber compositions and tires
WO2005042632A1 (fr) Composition de caoutchouc a base de dienes conjugues contenant de la silice et article moule
US20200207957A1 (en) High-grip tire rubber compositions
TWI845481B (zh) 高抓地力輪胎用橡膠組成物
JP4425653B2 (ja) シリカ充填ゴム組成物および成形体
JP2020204007A (ja) タイヤ
JP2004107384A (ja) 共役ジエン系ゴム、ゴム組成物、及び共役ジエン系ゴムの製造方法
WO2003064516A1 (fr) Composition de caoutchouc et son procede de production
JP3951755B2 (ja) ゴム組成物
JP6120949B2 (ja) 乳化重合共役ジエン系重合体とシリカ懸濁液とからなるゴム組成物およびその製造方法
JP6477226B2 (ja) 共役ジエン系ゴム組成物の製造方法
JP2015086307A (ja) 共役ジエン系ゴム組成物およびゴム架橋物
JP4117136B2 (ja) ゴム組成物及びそれを用いた空気入りタイヤ
WO2003070797A1 (fr) Caoutchouc dienique conjugue, caoutchouc etendu a l'huile et composition de caoutchouc
JP6753035B2 (ja) ゴム組成物
JP2008285555A (ja) ゴム組成物及びそれを用いた空気入りタイヤ
JP2003321578A (ja) 空気入りタイヤ
JP3970631B2 (ja) ゴム組成物及びそれを用いた空気入りタイヤ
JP4670132B2 (ja) 共役ジエン系重合体及びその製法
WO2025018210A1 (fr) Composition de caoutchouc pour parois latérales et paroi latérale

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase