US20160009835A1 - Catalyst for Conjugated Diene Polymerization, Conjugated Diene Polymer and Modified Conjugated Diene Polymer Produced Using the Same, Production Methods Thereof, Rubber Composition for Tire, and Rubber Composition for Rubber Belt - Google Patents

Catalyst for Conjugated Diene Polymerization, Conjugated Diene Polymer and Modified Conjugated Diene Polymer Produced Using the Same, Production Methods Thereof, Rubber Composition for Tire, and Rubber Composition for Rubber Belt Download PDF

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US20160009835A1
US20160009835A1 US14/775,961 US201414775961A US2016009835A1 US 20160009835 A1 US20160009835 A1 US 20160009835A1 US 201414775961 A US201414775961 A US 201414775961A US 2016009835 A1 US2016009835 A1 US 2016009835A1
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conjugated diene
polymerization
rubber
diene polymer
compound
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Koji Shiba
Masato Murakami
Michinori Suzuki
Naomi Okamoto
Mitsuharu Anbe
Masahiro Tanaka
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Ube Corp
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Ube Industries Ltd
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Assigned to UBE INDUSTRIES, LTD. reassignment UBE INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SUZUKI, MICHINORI, ANBE, MITSUHARU, OKAMOTO, NAOMI, TANAKA, MASAHIRO, MURAKAMI, MASATO, SHIBA, KOJI
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers 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
    • C08F136/04—Homopolymers 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
    • C08F136/06—Butadiene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/12—Incorporating halogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and 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
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and 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
    • C08F36/04—Homopolymers and 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
    • C08F36/06—Butadiene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/045—Fullerenes

Definitions

  • the present invention relates to a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound, a conjugated diene polymer and a modified conjugated diene polymer produced using the same, production methods thereof, a rubber composition for a tire, and a rubber composition for a rubber belt.
  • Various catalysts for a polymerization of a conjugated diene such as 1,3-butadiene and isoprene, have conventionally been proposed, and some of them have been industrialized.
  • a conjugated diene polymer having high cis-1,4 structures combinations of a compound of a metal such as titanium, cobalt, nickel or neodymium with an organic aluminum compound are often used.
  • Patent Literature 1 discloses a catalyst system including a salt of a rare earth metal, an organic metal compound of a group I to III element of the periodic table, and a fluorine-containing organic boron compound.
  • Patent Literature 2 discloses a polymerization catalyst including a compound of a group IIIB metal of the periodic table, an ionic compound of a non-coordinating anion and a cation, and an organic metal compound of a group I to III element of the periodic table.
  • Patent Literature 3 lists organic metal compounds including an element selected from groups 2, 12 and 13 of the periodic table.
  • Patent Literatures 4 to 6 report polymerizations of a conjugated diene using a metallocene type gadolinium complex.
  • Patent Literatures 1 to 3 are mainly neodymium-based catalysts, and gadolinium compounds have not yet been made clear.
  • the catalysts described in Patent Literatures 4 to 6 have defects that they have low catalytic activities of at most 540 g/mmol-Gd/hr.
  • a rubber composition containing a polybutadiene rubber (BR) or a styrene-butadiene rubber (SBR) as a main component, and including, in addition, a natural rubber, and the like has conventionally been industrially produced and used mainly as a material for a tire, a crawler for a crawler type traveling apparatus, an industrial rubber belt, or the like, utilizing its characteristic (Patent Literatures 7 and 8).
  • Patent Literature 9 discloses, as an example of a modification of a high cis-diene-based rubber, a method in which cis-1,4-polybutadiene is produced using a titanium compound having a cyclopentadienyl backbone as a catalyst, and then the product is modified by reacting it with 4,4′-bis(diethylamino)benzophenone, but the resulting product has a very small ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), (Mw/Mn), of less than 1.5, thus resulting in a problem of processability.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • a crawler type traveling apparatus which is used in every field, such as a bulldozer, is configured by winding an endless belt-shaped elastic crawler around a drive sprocket, an idler, and multiple trunk rollers. It is often used in harsher conditions than those in wheels, and crawler structures have been improved in order to increase a running performance and durability.
  • rubber compositions for a crawler which are tougher, have a higher durability, and are excellent in low fuel consumption are required.
  • a rubber composition used for a rubber belt it is required, for a rubber composition used for a rubber belt, to have a high tensile strength, a moderate hardness, a softness, an elasticity, a high flexibility, and a high impact resistance, and further energy saving and weight saving are also required.
  • reinforcement using an inorganic reinforcing agent or short fiber is proposed.
  • an inorganic reinforcing agent such as carbon black
  • dynamic heat generation is increased, and a problem in which the weight saving is not attained is raised because of an increased specific gravity of the formulation.
  • Patent Literature 8 has a problem in which the composition cannot necessarily obtain sufficient effects in the tensile stress and the elongation fatigue resistance, because microfine dispersion of 1,2-polybutadiene short fiber crystals in the butadiene rubber, which is a matrix component, is insufficient.
  • a vinyl•cis-polybutadiene in which syndiotactic 1,2-polybutadiene (hereinafter may sometimes be referred to as SPB) is dispersed in high cis-BR (hereinafter may sometimes be referred to as VCR) is known as a BR having higher functional characteristics, which utilizes the characteristics of the high cis-BR.
  • Patent Literatures 10 and 11 disclose methods for producing an SPB-containing high cis-BR composite using a cobalt catalyst.
  • Patent Literature 12 discloses a method for producing an SPB-containing high cis-BR composite using a nickel catalyst.
  • Patent Literature 13 discloses a method for producing VCR in an inert organic solvent including mainly a C 4 fraction such as n-butane, cis-2-butene, trans-2-butene, or butene-1.
  • a method for producing VCR using a gadolinium catalyst has not yet been reported.
  • the present invention has been made, and it is an object of the present invention to provide a catalyst for a conjugated diene polymerization containing a gadolinium compound, which can produce a conjugated diene polymer having a high content of cis-1,4 structures with a high activity.
  • VCR vinyl•cis-polybutadiene
  • a rubber composition for a tire and a tire which are tough, have excellent durability of an elongation fatigue resistance and an abrasion resistance, have a reduced energy loss, and can be used for a crawler; and a rubber composition for a rubber belt and a rubber belt, which are preferable for an industrial rubber belt.
  • the present inventors have intensively researched; as a result, they have found that when a non-metallocene type gadolinium compound is used, a conjugated diene polymer having a high content of cis-1,4 structures can be produced with a higher activity than those in conventional methods, and have reached the present invention.
  • conjugated diene polymer or the modified conjugated diene polymer described above a conjugated diene polymer composition having excellent rebound resilience and abrasion resistance, and a modified conjugated diene polymer composition having an excellent elongation fatigue resistance, in addition to the above, can be produced, and have reached the present invention.
  • VCR vinyl•cis-polybutadiene
  • a rubber composition for a tire and a tire using the conjugated diene polymer or the modified conjugated diene polymer are tough, have excellent durability of elongation fatigue resistance, abrasion resistance, and the like, have a reduced energy loss, and can be used for a crawler; and a rubber composition for a rubber belt and a rubber belt using the conjugated diene polymer or the modified conjugated diene polymer described above, are preferable for an industrial rubber belt, and have reached the present invention.
  • a catalyst for a conjugated diene polymerization including: a non-metallocene type gadolinium compound (A) represented by the following general formula (1); an ionic compound (B) formed of a non-coordinating anion and a cation; and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • an ionic compound (B) formed of a non-coordinating anion and a cation and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the organic metal compound (C) is preferably an organic aluminum compound, and the ionic compound (B) is preferably a boron-containing compound.
  • a method for producing a conjugated diene polymer including polymerizing a conjugated diene compound using the catalyst for a conjugated diene polymerization.
  • a method for producing a modified conjugated diene polymer including: polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polymer; and modifying the conjugated diene polymer with an amino group-containing carbonyl compound to obtain a modified conjugated diene polymer.
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • an ionic compound (B) formed of a non-coordinating anion and a cation and an organic metal compound (C) of an element selected from the group consisting of group 2, a group 12, and a group 13 of the periodic table
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the amino group-containing carbonyl compound is preferably a 4,4′-bis-dialkylaminobenzophenone, and it is preferable to adjust the molecular weight using a compound selected from (1) a hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organic metal compound in the polymerization of the conjugated diene compound.
  • a method for producing a modified conjugated diene polymer including: polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polymer; and modifying the conjugated diene polymer with a halogenated benzyl compound to obtain a modified conjugated diene polymer.
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • an ionic compound (B) formed of a non-coordinating anion and a cation and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the halogenated benzyl compound is preferably a piperonyl chloride, a dimethoxybenzyl bromide, or a methoxybenzyl chloride, and it is preferable to adjust the molecular weight with a compound selected from (1) a hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organic metal compound in the polymerization of the conjugated diene compound.
  • a method for producing a modified conjugated diene polymer which includes: polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table to obtain a conjugated diene polymer; and modifying the conjugated diene polymer with an aldehyde compound to obtain a modified conjugated diene polymer.
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • an ionic compound (B) formed of a non-coordinating anion and a cation and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the aldehyde compound is preferably a heliotropin or a veratrum aldehyde, and it is preferable to adjust the molecular weight with a compound selected from the group consisting of (1) a hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organic metal compound in the polymerization of the conjugated diene compound.
  • a method for producing a vinyl•cis-polybutadiene which includes performing a cis-1,4 polymerization of a 1,3-butadiene, and performing a subsequent syndiotactic-1,2 polymerization in the resulting polymerization system, wherein a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table is used as a catalyst in the cis-1,4 polymerization, and a catalyst system containing a sulfur compound is used as a catalyst in the syndiotactic-1,2 polymerization.
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the organic metal compound (C) is preferably an organic aluminum compound
  • the ionic compound (B) is preferably a boron-containing compound
  • vinyl•cis-polybutadiene obtained by a production method, which includes performing a cis-1,4 polymerization of 1,3-butadiene using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table; and performing a syndiotactic-1,2 polymerization using a catalyst system containing a sulfur compound in the resulting polymerization system.
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • an ionic compound (B) formed of a non-coordinating anion and a cation an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • a conjugated diene polymer composition including: a conjugated diene polymer ( ⁇ ) resulting from a polymerization of a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table; a diene polymer ( ⁇ ) other than the ( ⁇ ); and a rubber-reinforcing agent ( ⁇ ).
  • A non-metallocene type gadolinium compound represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the rubber-reinforcing agent ( ⁇ ) is preferably a carbon black, it is preferable to adjust the molecular weight of the conjugated diene compound with a compound selected from the group consisting of (1) a hydrogen, (2) a metal hydride compound, (3) a hydrogenated organic metal compound, and the conjugated diene compound is preferably a 1,3-butadiene.
  • a modified conjugated diene polymer composition including: a modified conjugated diene polymer ( ⁇ ′) obtained by polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), a ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table, and then modifying the resulting polymer with an amino group-containing carbonyl compound; a diene polymer ( ⁇ ) other than the ( ⁇ ′); and a rubber-reinforcing agent ( ⁇ ).
  • A non-metallocene type gadolinium compound represented by the following general formula (1)
  • a ionic compound (B) formed of a non-coordinating anion and a cation and an organic metal compound (C) of an
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the rubber-reinforcing agent ( ⁇ ) is preferably a carbon black
  • the amino group-containing carbonyl compound is preferably a 4,4′-bis-dialkylaminobenzophenone
  • the conjugated diene compound is preferably a 1,3-butadiene.
  • a rubber composition for a tire including: rubber components ( ⁇ )+( ⁇ ); and a rubber-reinforcing agent ( ⁇ ), wherein the rubber-reinforcing agent ( ⁇ ) is included in an amount of 30 to 80 parts by mass based on 100 parts by mass of the rubber components ( ⁇ )+( ⁇ ).
  • the rubber components ( ⁇ ) is a conjugated diene polymer ( ⁇ ) obtained by polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.
  • the rubber component ( ⁇ ) is a diene polymer ( ⁇ ) other than the ( ⁇ ).
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • a rubber composition for a tire including: rubber components ( ⁇ ′)+( ⁇ ); and a rubber-reinforcing agent ( ⁇ ), wherein the rubber-reinforcing agent ( ⁇ ) is included in an amount of 30 to 80 parts by mass based on 100 parts by mass of the rubber components ( ⁇ ′)+( ⁇ ).
  • the rubber component ( ⁇ ′) is a modified conjugated diene polymer ( ⁇ ′) obtained by polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.
  • the rubber component ( ⁇ ) is a diene polymer ( ⁇ ) other than the ( ⁇ ′).
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the diene polymer ( ⁇ ) other than the ( ⁇ ) and ( ⁇ ′) is preferably a natural rubber and/or a polyisoprene, and the rubber-reinforcing agent (F) is preferably a carbon black.
  • a rubber composition for a rubber belt including: rubber components ( ⁇ )+( ⁇ ); and a rubber-reinforcing agent ( ⁇ ), wherein the rubber-reinforcing agent ( ⁇ ) is included in an amount of 20 to 70 parts by mass based on 100 parts by mass of the rubber components ( ⁇ )+( ⁇ ).
  • the rubber component ( ⁇ ) is a conjugated diene polymer ( ⁇ ) obtained by polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.
  • the rubber component ( ⁇ ) is a diene polymer ( ⁇ ) other than the ( ⁇ ).
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • a rubber composition for a rubber belt including: rubber components ( ⁇ ′)+( ⁇ ); and a rubber-reinforcing agent ( ⁇ ), wherein the rubber-reinforcing agent ( ⁇ ) is included in an amount of 20 to 70 parts by mass based on 100 parts by mass of the rubber components ( ⁇ ′)+( ⁇ ).
  • the rubber component ( ⁇ ′) is a modified conjugated diene polymer ( ⁇ ′) obtained by polymerizing a conjugated diene compound using a catalyst for a conjugated diene polymerization containing a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table, and then modifying the resulting polymer.
  • the rubber component ( ⁇ ) is a diene polymer ( ⁇ ) other than the ( ⁇ ′).
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • the rubber-reinforcing agent ( ⁇ ) is preferably a carbon black and/or a silica, and it is more preferable that the rubber-reinforcing agent ( ⁇ ) is a carbon black and a silica and the silica is included in an amount of 70% by mass or less in the rubber-reinforcing agent.
  • a rubber belt using the rubber composition for a rubber belt as a rubber substrate.
  • a catalyst for a conjugated diene polymerization capable of producing a conjugated diene polymer having a high content of cis-1,4-structures with a high activity.
  • a conjugated diene polymer a modified conjugated diene polymer, and a vinyl•cis-polybutadiene (VCR), which have a very high content of cis-1,4 structures, using the catalyst which is easy to handle and have a high activity, and production methods thereof.
  • a conjugated diene polymer composition which has an improved filler dispersibility, and excellent rebound resilience and abrasion resistance, and a modified conjugated diene polymer composition, which has an excellent elongation fatigue resistance in addition to the above.
  • a rubber composition for a tire and a tire which are tough, have excellent durability of elongation fatigue resistance and abrasion resistance, have a reduced energy loss, and can be used for a crawler, and a rubber composition for a rubber belt and a rubber belt preferable for an industrial rubber belt.
  • FIG. 1 is a graph showing a relationship between a UV/RI value and (1/Mn) ⁇ 10 4 for obtaining a degree of modification of the modified conjugated diene polymer of the present invention.
  • UV denotes a peak area obtained from a UV absorbance at 274 nm obtained in a GPC measurement of a polymer
  • RI denotes a peak area obtained from a differential refractive index.
  • Mn denotes a number average molecular weight.
  • the non-metallocene type gadolinium compound (A) used in the catalyst for a conjugated diene polymerization in the present invention is a non-metallocene type gadolinium compound represented by the following general formula (1):
  • R 1 , R 2 , and R 3 each shows a hydrogen or a substituent having 1 to 12 carbon atoms, O shows an oxygen atom, and Gd shows a gadolinium atom.
  • substituent having 1 to 12 carbon atoms in R 1 to R 3 in the general formula (1) may include saturated hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group; unsaturated hydrocarbon groups such as a vinyl group, a 1-propenyl group,
  • the substituent may also include groups which are substituted by a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group or the like at any position.
  • saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.
  • non-metallocene type gadolinium compound (A) may include tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium, tris(2,6,6-trimethyl-3,5-heptanedionato)gadolinium, tris(2,6-dimethyl-3,5-heptanedionato)gadolinium, tris(3,5-heptanedionato)gadolinium, tris(2,4-pentanedionato)gadolinium, tris(2,4-hexanedionato)gadolinium, tris(1,5-dicyclopentyl-2,4-pentanedionato)gadolinium, tris(1,5-dicyclohexyl-2,4-pentanedionato)gadolinium, and the like.
  • preferable examples may include tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium, tris(2,6-dimethyl-3,5-heptanedionato)gadolinium, tris(2,4-pentanedionato)gadolinium, and the like. Particularly preferable examples may include tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium, and tris(2,6-dimethyl-3,5-heptanedionato)gadolinium.
  • the non-metallocene type gadolinium compound (A) may be used alone or as a mixture of two or more kinds.
  • the non-metallocene type gadolinium compound (A) can be used as a catalyst for a conjugated diene polymerization in combination with the ionic compound (B) including a non-coordinating anion and a cation, and the organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table.
  • the non-coordinating anion may include, for example, tetra(phenyl)borate, tetra(fluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis-trifluoromethylphenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetra(triyl)borate, tetra(xylyl)borate, triphenyl(pentafluorophenyl)borate, tris(pentafluorophenyl)(phenyl)borate, tridecahydride
  • the cation may include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, a ferrocenium cation, and the like.
  • the carbonium cation may include tri-substituted carbonium cations such as triphenylcarbonium cation, and tri-substituted phenylcarbonium cation.
  • the tri-substituted phenylcarbonium cation may include a tri(methylphenyl)carbonium cation, and a tri(dimethylphenyl)carbonium cation.
  • ammonium cation may include trialkylammonium cations such as a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, and a tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as an N,N-dimethylanilinium cation, an N,N-diethylanilinium cation, and an N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as a di(isopropyl)ammonium cation, and a dicyclohexylammonium cation.
  • trialkylammonium cations such as a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation,
  • the phosphonium cation may include allylphosphonium cations such as a triphenylphosphonium cation, a tetraphenylphosphonium cation, a tri(methylphenyl)phosphonium cation, a tetra(methylphenyl)phosphonium cation, a tri(dimethylphenyl)phosphonium cation, and a tetra(dimethylphenyl)phosphonium cation.
  • allylphosphonium cations such as a triphenylphosphonium cation, a tetraphenylphosphonium cation, a tri(methylphenyl)phosphonium cation, a tetra(methylphenyl)phosphonium cation, a tri(dimethylphenyl)phosphonium cation, and a tetra(dimethylphenyl)phosphonium cation.
  • any combination, obtained by arbitrarily selecting from the non-coordinating anions and the cations listed above respectively, may be preferably used as the ionic compound (B).
  • a boron-containing compound is preferable as the ionic compound (B), and triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(fluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and 1,1′-dimethylferrocenium tetrakis(pentafluorophenyl)borate are particularly preferable among them.
  • the ionic compound (B) may be used alone or as a mixture of two or more kinds.
  • an alumoxane may be used.
  • the alumoxane is a compound obtained by contacting an organic aluminum compound with a condensing agent, which includes a linear alumoxane or cyclic alumoxane represented by the general formula: (—Al(R′)O—), wherein R′ denotes a hydrocarbon group having 1 to 10 carbon atoms, including groups partially substituted by a halogen atom and/or an alkoxy group; and n is a degree of polymerization and 5 or more, preferably 10 or more.
  • R′ may include a methyl group, an ethyl group, a propyl group and an isobutyl group, and methyl group is preferable.
  • An organic aluminum compound used as a starting material of the alumoxane may include, for example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum, and mixtures thereof, and the like. Of these, an alumoxane obtained using a mixture of trimethyl aluminum and triisobutyl aluminum can be preferably used.
  • Typical condensing agent may be water, and in addition it may include any agent capable of causing a condensation reaction of the above-mentioned organic aluminum compound, for example, adsorbed water in an inorganic substance, diols, and the like.
  • an organic magnesium compound, an organic zinc compound, an organic aluminum compound, and the like are used.
  • Specific compounds thereof may include alkyl magnesium halides such as methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, butyl magnesium iodide, and hexyl magnesium iodide.
  • alkyl magnesium halides such as methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, butyl magnesium iodide, and hexyl magnesium iodide.
  • the compound may further include dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, and ethyl hexyl magnesium.
  • dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, and ethyl hexyl magnesium.
  • the compound may include dialkyl zinc such as dimethyl zinc, diethyl zinc, diisobutyl zinc, dihexyl zinc, dioctyl zinc, and didecyl zinc.
  • the compound may include trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum.
  • the compound may include dialkyl aluminum chlorides such as dimethyl aluminum chloride and diethyl aluminum chloride; organic aluminum halides such as ethyl aluminum sesqui-chloride and ethyl aluminum dichloride; hydrogenated organic aluminum compounds such as diethyl aluminum hydride, diisobutyl aluminum hydride, and ethyl aluminum sesqui-hydride.
  • dialkyl aluminum chlorides such as dimethyl aluminum chloride and diethyl aluminum chloride
  • organic aluminum halides such as ethyl aluminum sesqui-chloride and ethyl aluminum dichloride
  • hydrogenated organic aluminum compounds such as diethyl aluminum hydride, diisobutyl aluminum hydride, and ethyl aluminum sesqui-hydride.
  • the organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table may be used alone or as a mixture of two or more kinds.
  • the group 13 elements are preferable, and an organic aluminum compound is preferable among them.
  • examples thereof may include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and the like. Triethyl aluminum is particularly preferable.
  • the polymerization of the conjugated diene can be carried out using the catalyst including the components (A), (B), and (C) described above.
  • a molecular weight-adjusting agent of the obtained conjugated diene polymer may be added as long as the effects of the present invention are not impaired.
  • a compound selected from hydrogen, a metal hydride compound, and an organic metal compound may be used as the molecular weight-adjusting agent.
  • the metal hydride compound may include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, germane, lithium borohydride, sodium borohydride, lithium aluminum hydride, sodium aluminum hydride, and the like.
  • the hydrogenated organic metal compound may include alkyl borane such as methyl borane, ethyl borane, propylborane, butyl borane, and phenyl borane; dialkyl borane such as dimethyl borane, diethyl borane, dipropyl borane, dibutyl borane, diphenyl borane; alkyl aluminum dihydrides such as methyl aluminum dihydride, ethyl aluminum dihydride, propyl aluminum dihydride, butyl aluminum dihydride, and phenyl aluminum dihydride; dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, di-normal-butyl aluminum hydride, diisobutyl aluminum hydride, and diphenyl aluminum hydride; silanes such as methyl silane, ethyl silane, propyl silane, butyl silane, phenyl si
  • diisobutyl aluminum hydride and diethyl aluminum hydride are preferable, and diisobutyl aluminum hydride is particularly preferable.
  • each catalyst component may be previously aged and then used. It is especially preferable that the component (A) and the component (C) are aged.
  • the aging is preferably performed by mixing the component (A) and the component (C) in an inert solvent in the presence or absence of the conjugated diene compound monomers to be polymerized.
  • the ageing temperature is from ⁇ 50 to 120° C., preferably from ⁇ 10 to 95° C.
  • the ageing time is from 0.005 to 24 hours, preferably from 0.01 to 5 hours, particularly preferably from 0.02 to 1 hour.
  • each catalyst component may be supported on an inorganic compound or an organic polymer compound, and then the resulting product can be used.
  • the addition order of the catalyst components is not particularly limited, and the components may be added, for example, in the following orders:
  • the component (C) is added to an inert organic solvent in the presence or absence of the conjugated diene compound monomers to be polymerized, and then the component (A) and the component (B) are added in an arbitrary order.
  • the component (C) is added to an inert organic solvent in the presence or absence of the conjugated diene compound monomers to be polymerized, the molecular weight-adjusting agent is added, and then the component (A) and the component (B) are added in an arbitrary order.
  • the component (A) is added to an inert organic solvent in the presence or absence of the conjugated diene compound monomers to be polymerized, the component (C) and the molecular weight-adjusting agent are added in an arbitrary order, and then the component (B) is added.
  • the component (B) is added to an inert organic solvent in the presence or absence of the conjugated diene compound monomers to be polymerized, the component (C) and the molecular weight-adjusting agent are added in an arbitrary order, and then the component (A) is added.
  • the component (C) is added to an inert organic solvent in the presence or absence of the conjugated diene compound monomers to be polymerized, the component (A) and the component (B) are added in an arbitrary order, and then the molecular weight-adjusting agent is added.
  • the conjugated diene compound monomer which is a starting material, may include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl butadiene, 2-methyl pentadiene, 4-methyl pentadiene, 2,4-hexadiene, and the like.
  • conjugated diene compound monomers containing 1,3-butadiene as a main component are preferable.
  • the monomer component may be used alone, or as a mixture of two or more kinds.
  • the conjugated diene compound monomers to be polymerized may be a whole amount of the monomers or a part of the monomers.
  • a contact mixture of the component containing at least one of the components (A), (B), and (C), and the monomers may be mixed with the rest monomer or a solution of the rest monomer.
  • an olefin compound such as ethylene, propylene, allene, 1-butene, 2-butene, 1,2-butadiene, penetene, cyclopentene, hexene, cyclohexene, octene, cyclooctadiene, cyclododecatriene, norbornene, or norbornadiene may be included.
  • Polymerization methods are not particularly limited, and mass polymerizations (bulk polymerizations) using monomers of a conjugated diene compound such as 1,3-butadiene themselves as a polymerization solvent, or solution polymerizations are employed.
  • the solvent used in the solution polymerization may include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethyl benzene, and cumene; olefinic hydrocarbons such as the olefinic compounds described above, cis-2-butene, trans-2-butene, and the like.
  • benzene, toluene, xylene, cyclohexane, and a mixture of cis-2-butene and trans-2-butene are preferably used.
  • the solvent may be used alone or as a mixture of two or more kinds.
  • the polymerization temperature is preferably within a range of ⁇ 30 to 150° C., more preferably 0 to 100° C., particularly preferably 10 to 80° C.
  • the polymerization time is preferably from one minute to 12 hours, more preferably from 3 minutes to 5 hours, particularly preferably from 5 minutes to one hour.
  • the pressure inside the polymerization tank is released if necessary, and post-treatments such as washing and drying are performed.
  • the conjugated diene polymer obtained in the present invention is exemplified by a cis-1,4-polybutadiene containing preferably 94% or more, more preferably 98% or more, particularly preferably 98.5% or more, of cis-1,4 structures.
  • the [ ⁇ ] of the conjugated diene polymer can be controlled to preferably from 0.1 to 10, more preferably from 1 to 7, particularly preferably from 1.5 to 5.
  • the conjugated diene polymer obtained in the present invention has a number average molecular weight (Mn) of preferably 10000 to 1000000, more preferably 100000 to 700000, particularly preferably 150000 to 550000.
  • the conjugated diene polymer has a ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn), (Mw/Mn), of preferably 1.5 to 10, more preferably 1.5 to 7, particularly preferably 1.5 to 4.
  • Mw/Mn is small, the processability may sometimes worsen.
  • the conjugated diene polymer obtained in the present invention can be modified, and additional effects can be exhibited by the modification. It is preferable in the present invention to use a modifier which is at least one compound selected from the group consisting of amino group-containing carbonyl compounds, halogenated benzyl compounds, and aldehyde compounds.
  • Aminobenzophenone compounds are preferable as a carbonyl compound (preferably an aromatic carbonyl compound) having an amino group (preferably an aminoalkyl group having an alkyl group with 1 to 6 carbon atoms).
  • Specific compound examples thereof may include 4-dimethyl aminoacetophenone, 4-diethyl aminoacetophenone, 4-dimethyl aminopropiophenone, 4-diethyl aminopropiophenone, 1,3-bis(diphenylamino)-2-propanone, 1,7-bis(methylethylamino)-4-heptanone, 4-dimethyl aminobenzophenone, 4-diethyl aminobenzophenone, 4-dibutyl aminobenzophenone, 4-diphenylaminobenzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4,4′-bis(dibutylamino)benzophenone, 4,4′-bis(diphenyla
  • Alkoxybenzyl halide compounds are preferable as the halogenated benzyl compound.
  • Specific compound examples thereof may include methoxybenzyl chloride, methoxybenzyl bromide, methoxybenzyl iodide, ethoxybenzyl chloride, ethoxybenzyl bromide, ethoxybenzyl iodide, dimethoxybenzyl chloride, dimethoxybenzyl bromide, dimethoxybenzyl iodide, diethoxybenzyl chloride, diethoxybenzyl bromide, diethoxybenzyl iodide, piperonyl chloride, piperonyl bromide, piperonyl iodide, and the like.
  • methoxybenzyl chloride, dimethoxybenzyl bromide, and piperonyl chloride are particularly preferable.
  • the modifier may be used alone or as a mixture of two or more kinds.
  • Aromatic aldehyde compounds are preferable as the aldehyde compound. Specific compound examples thereof may include methoxybenzaldehyde, ethoxybenzaldehyde, propoxybenzaldehyde, butoxybenzaldehyde, veratrum aldehyde, 2,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, diethoxybenzaldehyde, ethoxymethoxybenzaldehyde, trimethoxybenzaldehyde, heliotropin, and the like. Of these compounds, veratrum aldehyde and heliotropin are particularly preferable.
  • the modifier may be used alone or as a mixture of two or more kinds.
  • Any solvent may be freely used as an organic solvent used in the modification reaction so long as it is not reacted with the conjugated diene polymer.
  • the same solvent as that used in the production of the conjugated diene polymer is usually used.
  • Specific examples thereof may include aromatic hydrocarbon solvents such as benzene, chlorobenzene, toluene, and xylene; aliphatic hydrocarbon solvents having 5 to 10 carbon atoms such as n-heptane, n-hexane, n-pentane, and n-octane; alicyclic hydrocarbon solvents such as cyclohexane, methyl cyclohexane, tetralin, and decalin, and the like. Methylene chloride and tetrahydrofuran may also be used.
  • the temperature of the reaction solution in the modification reaction is within a range of preferably 0 to 100° C., particularly preferably 30 to 90° C. When the temperature is too low, the modification reaction slowly proceeds, whereas when the temperature is too high, the polymer is likely to cause gelation.
  • the time of the modification reaction is not particularly limited, and it is within a range of preferably one minute to 5 hours, more preferably 3 minutes to one hour. When the modification reaction time is too short, the reaction proceeds insufficiently, whereas when the time is too long, the polymer is likely to cause gelation.
  • the amount of the conjugated diene polymer in the modification reaction solution is within a range of usually 5 to 500 g per liter of the solvent, preferably 20 to 300 g, further more preferably 30 to 200 g.
  • the amount of the modifier used in the modification reaction is within a range of usually 0.01 to 150 millimoles per 100 g of the conjugated diene polymer, preferably 0.1 to 100 millimoles, further more preferably 0.2 to 50 millimoles.
  • the amount used is too small, the amount of the modified groups introduced into the modified conjugated diene polymer becomes small, and thus only a small modifying effect is exhibited.
  • the amount used is too large, an unreacted modifier, undesirably, remains in the modified conjugated diene polymer and the removal thereof takes labor.
  • the modification reaction is performed by the following methods: a method in which after the polymerization reaction, the modifier and then a polymerization terminator are added thereto, and the solvent and unreacted monomers remaining the reaction product are removed in a steam stripping method or a vacuum drying method; a method in which after the addition of a polymerization terminator, the modifier is added thereto; a method in which after the dried polymer is resolved in a solvent, the modifier and a catalyst are added thereto, and the like.
  • some polymerization terminators may reduce the activity of that site of the polymer which is reacted with the modifier, depending on the kind of the polymerization terminator, methods in which the modifier is added before the polymerization is stopped are preferable.
  • the degree of modification of the modified conjugated diene polymer is calculated using a gel permeation chromatography (GPC) measurement.
  • GPC gel permeation chromatography
  • a vertical axis shows a value of UV/RI, a ratio of a peak area UV determined from a UV absorbance at 274 nm of a polymer, obtained from a GPC measurement, and a peak area RI obtained from a differential refractive index (RI).
  • a horizontal axis represents a value of (1/Mn) ⁇ 10 4 , wherein Mn is a number average molecular weight.
  • Li-BR unmodified represents a line obtained by plotting UV/RI values of a polymer itself obtained by polymerizing 1,3-butadiene according to a living anionic polymerization using an Li catalyst, relative to a polymer having a different number average molecular weight Mn, which can be approximated to a straight line.
  • Li-BR (modified) is a line obtained by plotting, relative to a polymer having a different number average molecular weight Mn, UV/RI values of a polymer obtained by performing a living anionic polymerization using an Li catalyst, and then modifying the resulting product by reacting polymerization terminals with a pre-determined modifier, which can be approximated to a straight line.
  • a difference between a UV/RI value on the Li-BR (modified) and a UV/RI value on the Li-BR (unmodified) at a certain number average molecular weight (Mn 1) is defined as A.
  • the difference shows a variation in the UV/RI value when one molecular chain having the number average molecular weight (Mn 1) is reacted with one molecule of the modifier, and thus a degree of modification can be calculated based on the value described above.
  • UV/RI values are calculated respectively for a modified cis-1,4-polybutadiene having a certain number average molecular weight (Mn 1) of the present invention, and a non-modified cis-1,4-polybutadiene obtained by the same manner as that of the modified polymer above, and a difference between them is defined as B.
  • Mn 1 number average molecular weight
  • B non-modified cis-1,4-polybutadiene obtained by the same manner as that of the modified polymer above, and a difference between them is defined as B.
  • the degree of modification of the modified cis-1,4-polybutadiene of the present invention is shown by the following formula:
  • the degree of modification of the modified conjugated diene polymer of the present invention is not particularly limited, and it is preferably more than 0.1, more preferably more than 0.5, further more preferably more than 0.7.
  • the degree of modification is also preferably less than 20, more preferably less than 15, further preferably less than 10.
  • the degree of modification is 0.1 or less, the effects obtained by the modification may sometimes be insufficient; whereas when the degree of modification is 20 or more, the original properties of the conjugated diene polymer may sometimes be deteriorated.
  • dispersibility of filler can be improved in a rubber due to an interaction of polar groups of the modifier groups (an amino group, an alkoxy group, and the like) with polar groups of the filler.
  • a method for producing a polybutadiene including a cis-1,4 polymerization of a 1,3-butadiene, and then a syndiotactic-1,2 polymerization in the resulting polymerization system wherein a catalyst for a conjugated diene polymerization (the catalyst for a conjugated diene polymerization of the present invention) including a non-metallocene type gadolinium compound (A) represented by the following general formula (1), an ionic compound (B) formed of a non-coordinating anion and a cation, and an organic metal compound (C) of an element selected from the group consisting of a group 2, a group 12, and a group 13 of the periodic table is used as a catalyst for the cis-1,4 polymerization, and a catalyst system containing a sulfur compound is used as a catalyst for the syndiotactic-1,2 polymerization, to obtain a vinyl•cis-poly
  • the component (A), the gadolinium compound, of the cis-1,4 polymerization catalyst system in the present invention is preferably a non-metallocene type gadolinium compound represented by the general formula (1) described above, but other gadolinium compounds may be used so long as they are soluble in a non-polar organic solvent. Examples thereof may include gadolinium salts, halogenated gadolinium, gadolinium alkoxides, non-metallocene type gadolinium complexes, and the like.
  • the gadolinium salt described above may include, for example, gadolinium acetate, gadolinium oxalate, gadolinium nitrate, gadolinium hydroxide, and the like.
  • the halogenated gadolinium described above may include, for example, gadolinium fluoride, gadolinium chloride, gadolinium bromide, gadolinium iodide, and the like.
  • the gadolinium alkoxide described above may include, for example, trimethoxygadolinium, triethoxygadolinium, tripropoxygadolinium, triisopropoxygadolinium, tributoxygadolinium, and the like.
  • a cis-1,4-polybutadiene having 90% or more, more preferably 92% or more, particularly preferably 96% or more, of cis-1,4 structures is preferable.
  • the [ ⁇ ] of the cis-1,4 polymerization component can be controlled to preferably from 0.1 to 10.0, more preferably from 1.0 to 7.0, particularly preferably from 1.5 to 5.0.
  • the syndiotactic-1,2 polymerization is performed in this polymerization system.
  • 1,3-butadiene may be or may not be newly added thereto.
  • a catalyst system containing a sulfur compound as a catalyst in the syndiotactic-1,2 polymerization.
  • a catalyst system including a trialkyl aluminum compound represented by R 1 3 Al wherein R 1 shows a hydrocarbon group having 1 to 10 carbon atoms, a sulfur compound, or a cobalt compound is preferably used as the catalyst for the syndiotactic-1,2 polymerization.
  • the trialkyl aluminum compound represented by R 1 3 Al may include triethyl aluminum, trimethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and the like. Of these, triethyl aluminum is preferable.
  • the sulfur compound may include carbon disulfide, phenyl isothiocyanate, xanthogenic acid compounds, and the like. Of these, carbon disulfide is preferable.
  • Salts and complexes of cobalt are preferably used as the cobalt compound.
  • Particularly preferable examples thereof may include cobalt salts such as cobalt chloride, cobalt bromide, cobalt nitride, cobalt 2-ethyl hexanate, cobalt naphthenate, cobalt acetate, and cobalt malonate; bis-acetylacetonate or tris-acetylacetonate of cobalt; ethyl acetoacetate cobalt; triallyl phosphine complexes, trialkyl phosphine complexes, organic base complexes such as pyridine complexes and picoline complexes of a halogenated cobalt; ethyl alcohol complexes of a halogenated cobalt, and the like.
  • cobalt 2-ethyl hexanate is preferable.
  • the trialkyl aluminum compound is contained in an amount of preferably 0.1 millimoles or more per mole of the 1,3-butadiene, particularly preferably 0.5 to 50 millimoles.
  • the cobalt compound is contained in an amount of preferably 0.001 millimoles or more per mole of the 1,3-butadiene, particularly preferably 0.01 to 1 millimole.
  • the concentration of the sulfur compound is 20 millimoles/L or less, particularly preferably 0.01 to 10 millimoles/L. Water may be or may not be added to the syndiotactic-1,2 polymerization, and when water is added, the amount thereof is 1.1 millimoles or less per millimole of the trialkyl aluminum compound, preferably 1 millimole or less.
  • the 1,2-polymerization of the 1,3-butadiene is performed at a temperature within a range of 0 to 100° C., preferably 10 to 100° C., further more preferably 20 to 100° C.
  • a yield of the 1,2-polybutadiene can be increased in the 1,2-polymerization.
  • the polymerization time (the average retention time) is within a range of preferably 10 minutes to 2 hours.
  • the polymerization tank is used alone or two or more tanks are connected.
  • the polymerization is performed by stirring and mixing the polymerization solution in the polymerization tank (the polymerization vessel).
  • a polymerization tank equipped with a stirrer for liquid with a high viscosity for example an apparatus described in JP-40-2645 B, can be used as the polymerization tank used in the 1,2-polymerization, because the viscosity is increased during the 1,2-polymerization and the polymer easily adheres.
  • a known antioxidant may be added in a conventional method.
  • the antioxidant may include phenol antioxidants such as 2,6-di-t-butyl-p-cresol (BHT), phosphorus antioxidants such as trinonylphenyl phosphite (TNP), sulfur oxidants such as dilauryl-3,3′-thiodipropionate (TPL), and the like.
  • BHT 2,6-di-t-butyl-p-cresol
  • TNP trinonylphenyl phosphite
  • TPL sulfur oxidants
  • the antioxidant may be used alone or as a mixture.
  • the antioxidant is added in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the vinyl•cis-polybutadiene.
  • a polymerization terminator is added to the polymerization system to stop the polymerization.
  • the polymerization solution is supplied to a tank for stopping the polymerization, and a large amount of an alcohol such as methanol or ethanol or a polar solvent such as water is poured into the polymerization solution; and in which an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid or benzoic acid, or hydrogen chloride gas is introduced into the polymerization solution.
  • an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid or benzoic acid, or hydrogen chloride gas is introduced into the polymerization solution.
  • the produced vinyl•cis-polybutadiene is separated, washed and dried according to a conventional method.
  • the thus obtained vinyl•cis-polybutadiene contains 3 to 30% by weight of (I) a boiling n-hexane-insoluble component (H.I.), and 97 to 70% by weight of (II) a boiling n-hexane-soluble component.
  • the boiling n-hexane-soluble component is a cis-1,4-polybutadiene having 90% or more of microstructures.
  • the H.I. is an SPB having a melting point of 180 to 215° C.
  • ML is from 20 to 200 at 100° C., preferably from 25 to 100, more preferably from 30 to 70.
  • the syndiotactic 1,2-polybutadiene dispersed in the vinyl•cis-polybutadiene is uniformly dispersed in the matrix of the cis-1,4-polybutadiene as fine crystals.
  • the conjugated diene polymer composition of the present invention includes preferably a conjugated diene polymer ( ⁇ ), and a diene polymer ( ⁇ ) other than the ( ⁇ ), and a rubber-reinforcing agent ( ⁇ ).
  • the modified conjugated diene polymer composition of the present invention includes preferably a modified conjugated diene polymer ( ⁇ ′), a diene polymer ( ⁇ ) other than the ( ⁇ ′), and a rubber-reinforcing agent ( ⁇ ).
  • the conjugated diene polymer or the modified conjugated diene polymer of the present invention alone or blended with another synthetic rubber or natural rubber, which is subjected to an oil extension with a process oil if necessary, is added with a filler such as carbon black, a vulcanizing agent, a vulcanization accelerator, and other compounding agents usually used to vulcanize it. It is used as an application of rubber requiring mechanical properties and abrasion resistance such as a tire, a hose, a belt, and other various industrial products. It also can be used as a modifier for plastic materials.
  • the ( ⁇ ) component, the rubber-reinforcing agent, used in the present invention may include inorganic reinforcing agents such as various carbon blacks, silica, activated calcium carbonate, and ultrafine particles of magnesium silicate.
  • the carbon black has preferably a particle size of 90 nm or less and a dibutyl phthalate (DBP) oil absorption of 70 ml/100 g or more.
  • DBP dibutyl phthalate
  • Examples thereof may include FEF, FF, GPF, SAF, ISAF, SRF, HAF, and the like.
  • the mixing proportion of the conjugated diene polymer composition and the modified conjugated diene polymer composition of the present invention it is preferable that 100 parts by weight of the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ) are mixed with 20 to 120 parts by weight of the rubber-reinforcing agent ( ⁇ ).
  • the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ) are formed of 90 to 5 parts by weight of the conjugated diene polymer composition ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) and 10 to 95 parts by weight of the diene polymer ( ⁇ ) other than the ( ⁇ ) or ( ⁇ ′).
  • the diene polymer ( ⁇ ) other than the ( ⁇ ) or ( ⁇ ′), contained in the conjugated diene polymer composition or the modified conjugated diene polymer composition is preferable a vulcanizable rubber, and specific examples thereof may include ethylene propylene diene rubber (EPDM), nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), polyisoprene, high cis-polybutadiene rubber, low cis-polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated butyl rubber, acrylonitrile-butadiene rubber, and the like.
  • EPDM ethylene propylene diene rubber
  • NBR nitrile rubber
  • IIR butyl rubber
  • CR chloroprene rubber
  • SBR styrene-butadiene rubber
  • SBR styrene-butadiene copolymer rubber obtained by a solution polymerization (S-SBR) is particularly preferable.
  • S-SBR solution polymerization
  • the rubber may be used alone or as a mixture of two or more kinds.
  • plastic materials such as an impact-resistant polystyrene
  • an impact-resistant polystyrene resin composition or rubber-modified impact-resistant polystyrene resin composition can be produced.
  • the conjugated diene polymer composition and the modified conjugated diene polymer composition of the present invention can be preferably used as a rubber composition for a tire and a rubber composition for a rubber belt by adjusting a mixing ratio of the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ) and the rubber-reinforcing agent ( ⁇ ).
  • the rubber composition for a tire contains the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ) of the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) and the diene polymer ( ⁇ ) other than the ( ⁇ ) or ( ⁇ ′), and the rubber-reinforcing agent ( ⁇ ), and it is preferable that the rubber-reinforcing agent ( ⁇ ) is contained in an amount of 30 to 80 parts by mass based on 100 parts by mass of the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ).
  • the diene polymer ( ⁇ ) other than the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) is used, and it is preferable to blend the diene polymer ( ⁇ ) other than the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) in an amount of 10 to 95 parts by mass based on 90 to 5 parts by mass of the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′). At least one of the natural rubber and the polyisoprene is preferably used as the diene polymer ( ⁇ ).
  • the rubber-reinforcing agent ( ⁇ ) blended with the rubber composition for a tire of the present invention may include various carbon blacks, silica, activated calcium carbonate, ultrafine particles of magnesium silicate, talc, mica, and the like. Of these, at least one of carbon black and silica is preferable.
  • a carbon black having a particle size of 90 nm or less and a dibutyl phtharate (DBP) oil absorption of 70 ml/100 g or more is particularly preferable.
  • DBP dibutyl phtharate
  • fullerene described in JP 2006-131819 may be used as the rubber-reinforcing agent ( ⁇ ) blended with the rubber composition for a tire.
  • the fullerene may include C60, C70, a mixture of C60 and C70, and derivatives thereof.
  • the fullerene derivative may include PCBM (Phenyl C61-butyric acid methyl ester), PCBNB (Phenyl C61-butyric acid n-butyl ester), PCBIB (Phenyl C61-butyric acid I-butyl ester), C70 PCBM (Phenyl C71-butyric acid methyl ester), and the like.
  • PCBM Phhenyl C61-butyric acid methyl ester
  • PCBNB Phenyl C61-butyric acid n-butyl ester
  • PCBIB Phenyl C61-butyric acid I-butyl ester
  • C70 PCBM Phenyl C71-butyric acid methyl ester
  • fullerene hydroxide, fullerene oxide, hydrogenated fillerene and the like may be used.
  • the rubber-reinforcing agent ( ⁇ ) is blended in an amount of 30 to 80 parts by mass, based on 100 parts by mass of the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ), which are formed of the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) and the diene polymer ( ⁇ ) other than the (a) or ( ⁇ ′), preferably 40 to 70 parts by mass.
  • a rubber component including the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′), the diene polymer ( ⁇ ) other than the ( ⁇ ) or ( ⁇ ′), and the rubber-reinforcing agent ( ⁇ ), has a JIS A hardness of preferably 55 to 80°, particularly preferably 60 to 75°.
  • the rubber composition for a belt includes the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ), which are formed of the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) and the diene polymer ( ⁇ ) other than the ( ⁇ ) or ( ⁇ ′), and the rubber-reinforcing agent ( ⁇ ), and it is preferable that the rubber-reinforcing agent ( ⁇ ) is included in an amount of 20 to 70 parts by mass based on 100 parts by mass of the rubber components ( ⁇ )+( ⁇ ).
  • the diene polymer ( ⁇ ) other than the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) is used, and it is preferable to blend the diene polymer ( ⁇ ) other than the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) in an amount of 10 to 95 parts by mass based on 90 to 5 parts by mass of the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′). At least one of the natural rubber and the polyisoprene is preferably used as the diene polymer ( ⁇ ).
  • the rubber-reinforcing agent ( ⁇ ) blended with the rubber composition for a belt of the present invention may include various carbon blacks, silica, activated calcium carbonate, ultrafine particles of magnesium silicate, talc, mica, and the like. Of these, at least one of carbon black and silica is preferable.
  • a carbon black having a particle size of 90 nm or less and a dibutyl phtharate (DBP) oil absorption of 70 ml/100 g or more is particularly preferable.
  • DBP dibutyl phtharate
  • the rubber-reinforcing agent ( ⁇ ) is blended in an amount of 20 to 70 parts by mass, preferably 30 to 60 parts by mass, based on 100 parts by mass of the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ), which are formed of the conjugated diene polymer ( ⁇ ) or the modified conjugated diene polymer composition ( ⁇ ′) and the diene polymer ( ⁇ ).
  • the rubber composition for a tire or the rubber composition for a rubber belt according to the present invention can be obtained by kneading the components described above through a usually used Banbury kneader, open roll, kneader, or twin screw kneader.
  • the rubber composition for a tire or the rubber composition for a rubber belt may be kneaded with compounding agents usually used in the rubber field, such as a vulcanizing agent, a vulcanization aid, an antioxidant, a filler, a process oil, zinc white, and stearic acid.
  • compounding agents usually used in the rubber field such as a vulcanizing agent, a vulcanization aid, an antioxidant, a filler, a process oil, zinc white, and stearic acid.
  • vulcanizing agent known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, metal oxides such as magnesium oxide are used.
  • the vulcanizing agent is preferably blended in an amount of about 0.5 to 3 parts by weight based on 100 parts by weight of the rubber components ( ⁇ )+( ⁇ ) or ( ⁇ ′)+( ⁇ ).
  • vulcanization aid known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, and xanthates are used.
  • the antioxidant may include amine-ketone antioxidants, imidazole antioxidants, amine antioxidants, phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
  • the filler may include inorganic fillers such as calcium carbonate, basic magnesium carbonate, clay, Lissajous, and diatomaceous earth, and organic fillers such as regenerated rubber and powdery rubber.
  • inorganic fillers such as calcium carbonate, basic magnesium carbonate, clay, Lissajous, and diatomaceous earth
  • organic fillers such as regenerated rubber and powdery rubber.
  • any of aromatic oil, naphthene oil, and paraffin oil may be used.
  • Measurement of Gd Content The measurement was performed according to an ICP emission spectrometry. In the measurement, Vista MPX, manufactured by Barian Japan KK, was used.
  • Intrinsic Viscosity [ ⁇ ] The viscosity was measured at 30° C. using a toluene solution of a polymer.
  • Productivity It shows a polymer yield (g) per mmol of a central metal of a catalyst used in a polymerization reaction, per hour of a polymerization time.
  • a catalyst is a gadolinium compound
  • it is a polymer yield (g) per mmol of gadolinium metal in the gadolinium compound used in a polymerization reaction, per hour of a polymerization time.
  • Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw) A molecule weight distribution curve was obtained according to a method using GPC (manufactured by Shimadzu Corporation), in which polystyrene as a standard substance and tetrahydrofuran as a solvent were used, at a temperature of 40° C., and calculation was performed using a calibration curve obtained from the molecule weight distribution curve to obtain a number average molecular weight and a weight average molecular weight.
  • Molecule Weight Distribution It was evaluated by a ratio of Mw/Mn, a weight average molecular weight Mw to a number average molecular weight Mn, which were obtained from GPC using polystyrene as the standard substance.
  • Mooney Viscosity (ML 1+4 , 100° C.): The viscosity was obtained in accordance with JIS-K 6300 by pre-heating a rubber at 100° C. for one minute and then measuring the viscosity for 4 minutes using a Mooney viscometer, manufactured by Shimadzu Corporation. The obtained value was shown as a Mooney viscosity of the rubber (ML 1+4 , 100° C.)
  • DSC Differential Scanning calorimetry
  • the content was obtained from a fusion heat amount measured by using a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation), and an H. I. calibration curve obtained in an actual H. I. measurement.
  • the actual value of H. I. was a remaining extract amount in parts by weight after 2 g of vinyl•cis-polybutadiene rubber was extracted with boiling in 200 ml of n-hexane for 4 hours in a Soxhlet's extractor.
  • Tensile Strength The strength was measured in accordance with JIS K 6252, and was shown as an index relative to a value in Comparative Examples, described in each Table, defined as 100 (the higher the index, the better the tensile strength).
  • Tensile Stress A 100% tensile stress and a 300% tensile stress were measured in accordance with JIS K 6251, and were shown as an index relative to a value in Comparative Example, described in each Table, defined as 100 (the higher the index, the better the tensile stress).
  • Rebound Resilience The rebound resilience was measured in accordance with JIS K 6255 using a Dunlop tripsometer at room temperature, and was shown as an index relative to a value in Comparative Example, described in each Table, defined as 100 (the higher the index, the better the rebound resilience).
  • Elongation Fatigue Resistance Using a fixed elongation tester (manufactured by Ueshima Seisakusho Co., Ltd.), a test specimen, which was a dumbbell-shaped No. 3 (JIS-K 6251) specimen having a 0.5 mm-cut at the central part, was broken under conditions of an initial strain of 50% and 300 times/minute. And the breaking number of times was determined. The results were shown as an index relative to a value in Comparative Example, described in each Table, defined as 100 (the higher the index, the better the elongation fatigue resistance).
  • a Lambourn abrasion resistance was measured in accordance with JIS-K 6264 at a slip rate of 20% or 40%, and is shown as an index relative to a value in Comparative Example, described in each Table, defined as 100 (the higher the index, the better the abrasion resistance).
  • MPT processability measuring apparatus
  • G′ Strain-Dependency of Storage Elastic Modulus
  • Example 1 wherein polymerization was performed in the same conditions as in those in Comparative Example 1 except for the catalyst (in particular, the central metal), the productivity is high, and the obtained polymer has a high content of cis-1,4 structures.
  • a polymerization was performed in the same manner as in Example 40, except that the pressure of the hydrogen gas was adjusted to 0.15 MPa.
  • the polymerization results are shown in Table 3.
  • a polymerization was performed in the same manner as in Example 40, except that the pressure of the hydrogen gas was adjusted to 0.20 MPa.
  • the polymerization results are shown in Table 3.
  • a polymerization was performed in the same manner as in Example 45, except that the pressure of the hydrogen gas was adjusted to 0.10 MPa.
  • the polymerization results are shown in Table 3.
  • a polymerization was performed in the same manner as in Example 45, except that the pressure of the hydrogen gas was adjusted to 0.15 MPa.
  • the polymerization results are shown in Table 3.
  • An inside of an autoclave with an inner capacity of 2 L was substituted by nitrogen, and a solution including 260 ml of a toluene solvent and 140 ml of butadiene was filled therein. After the temperature of the solution was elevated to 30° C., 3.0 ml of a toluene solution (2 mol/L) of triethyl aluminum (TEAL) was added thereto.
  • TEAL triethyl aluminum
  • Example 34 in which the polymerization was performed in conditions which are the closest to those in Comparative Example 2, the productivity is significantly high, such as more than twice that in Comparative Example 2, and the obtained polymer had a very high content of cis-1,4 structures.
  • the recovered polybutadiene was dried in vacuo at 80° C. for 3 hours.
  • the recovered polybutadiene had a melting point, according to the DSC measurement, of ⁇ 8.4° C., and had a fusion heat amount of 43.5 J/g.
  • Other polymerization results are shown in Table 5.
  • the recovered polybutadiene was dried in vacuo at 80° C. for 3 hours.
  • the recovered polybutadiene had a melting point, according to the DSC measurement, of ⁇ 6.6° C., and a fusion heat amount of 45.6 J/g.
  • Other polymerization results are shown in Table 5.
  • An inside of an autoclave with an inner capacity of 1.5 L was substituted by nitrogen, and a solution including 245 ml of a cyclohexane solvent and 250 ml of butadiene was filled therein, to which 0.5 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added thereto.
  • a solution including 245 ml of a cyclohexane solvent and 250 ml of butadiene was filled therein, to which 0.5 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added thereto.
  • TEAL triethyl aluminum
  • An inside of an autoclave with an inner capacity of 1.5 L was substituted by nitrogen, and a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 1.25 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 1.25 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • TEAL triethyl aluminum
  • a cyclohexane solution (1 mol/L) of triethyl aluminum (TEA) and 9.0 ⁇ l of water were added, to which 10.0 ml of a cyclohexane solution (0.005 mol/L) of cobalt octylate (Co(Oct) 2 ) and 0.3 ml of a cyclohexane solution (1 mol/L) of carbon disulfide (CS 2 ) were added.
  • a polymerization was performed at 50° C. for 15 minutes, and then 3 ml of an ethanol/heptane (1/1) solution containing an antioxidant was added to stop the polymerization.
  • An inside of an autoclave with an inner capacity of 1.5 L was substituted by nitrogen, and a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 2.0 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • TEAL triethyl aluminum
  • a cyclohexane solution (1 mol/L) of triethyl aluminum (TEA) and 9.0 ⁇ l of water were added, to which 5.0 ml of a cyclohexane solution (0.005 mol/L) of cobalt octylate (Co(Oct) 2 ) and 0.3 ml of a cyclohexane solution (1 mol/L) of carbon disulfide (CS 2 ) were added.
  • a polymerization was performed at 50° C. for 15 minutes, and then 3 ml of an ethanol/heptane (1/1) solution containing an antioxidant was added to stop the polymerization.
  • An inside of an autoclave with an inner capacity of 1.5 L was substituted by nitrogen, and a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 2.5 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • TEAL triethyl aluminum
  • a cyclohexane solution (1 mol/L) of triethyl aluminum (TEA) and 9.0 ⁇ l of water were added, to which 0.35 ml of a cyclohexane solution (0.1 mol/L) of cobalt octylate (Co(Oct) 2 ) and 0.3 ml of a cyclohexane solution (1 mol/L) of carbon disulfide (CS 2 ) were added.
  • a polymerization was performed at 50° C. for 15 minutes, and then 3 ml of an ethanol/heptane (1/1) solution containing an antioxidant was added to stop the polymerization.
  • An inside of an autoclave with an inner capacity of 1.5 L was substituted by nitrogen, and a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 2.5 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • TEAL triethyl aluminum
  • a cyclohexane solution (1 mol/L) of triethyl aluminum (TEA) and 9.0 ⁇ l of water were added, to which 0.3 ml of a cyclohexane solution (0.1 mol/L) of cobalt octylate (Co(Oct) 2 ) and 1.0 ml of a cyclohexane solution (1 mol/L) of carbon disulfide (CS 2 ) were added.
  • a polymerization was performed at 50° C. for 15 minutes, and then 3 ml of an ethanol/heptane (1/1) solution containing an antioxidant was added to stop the polymerization.
  • An inside of an autoclave with an inner capacity of 1.5 L was substituted by nitrogen, and a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 1.25 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • a solution including 245 ml of cyclohexane and 250 ml of butadiene was filled therein, to which 1.25 ml of a cyclohexane solution (2 mol/L) of triethyl aluminum (TEAL) was added.
  • TEAL triethyl aluminum
  • An inside of an autoclave with an inner capacity of 1.6 L was substituted by nitrogen, and 700 ml of a mixed solution including 30% by weight of butadiene, 41% by weight of cyclohexane, and 29% by weight of 2-butene was filled therein, to which 0.7 ml of a cyclohexane solution (0.25 mol/L) of carbon disulfide (CS 2 ) was added and water (H 2 O) was added so that a concentration was 2.4 mmol/L, at room temperature, and the mixture was stirred at 25° C. for 30 minutes at 400 rpm.
  • CS 2 carbon disulfide
  • a toluene solution (1 mol/L) of triethyl aluminum (TEA) was added, to which 1.0 mmol/L of water (H 2 O) was added, followed by adding 1.8 ml of a toluene solution (0.05 mol/L) of cobalt octylate (Co(Oct) 2 ) and 0.36 ml of a toluene solution (1 mol/L) of carbon disulfide (CS 2 ), and the polymerization was performed at 40° C. for 10 minutes. 5 ml of an ethanol/heptane (1/1) solution containing an antioxidant was added to stop the polymerization.
  • TSA triethyl aluminum
  • the recovered polybutadiene was dried in vacuo at 80° C. for 3 hours.
  • the recovered polybutadiene had a melting point, according to the DSC measurement of polybutadiene, of ⁇ 8.4° C., and a fusion heat amount of 43.5 J/g.
  • Other polymerization results are shown in Table 9.
  • the recovered polybutadiene was dried in vacuo at 80° C. for 3 hours.
  • the recovered polybutadiene had a melting point, according to the DSC measurement of polybutadiene, of ⁇ 6.6° C., and a fusion heat amount of 45.6 J/g.
  • Other polymerization results are shown in Table 9.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 11.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 11.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 12.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 12.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 13.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 13.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 13.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 13.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Tables 11 to 13.
  • Stearic acid Stearic acid, Kao Corporation
  • Antioxidant Antigen 6C, Sumitomo Chemical Co., Ltd.
  • Vulcanization accelerator Nocceler NS, Ouchi Shinko Chemical Industrial Co.
  • Sulfur Sulfur, Hosoi Kagaku Kogyo Kabushiki Kaisha
  • Example 85 Example 86 Tensile stress 100 103 107 (50%) Tensile stress 100 105 107 (100%) Tensile stress 100 106 104 (300%) Rebound 100 106 107 Resilience Lambourn 100 106 107 abrasion (20% Slip) Lambourn 100 103 106 abrasion (40% Slip) Low exothermic 100 111 105 property Permanent set 100 128 123 tan ⁇ (30° C.) 100 109 105 tan ⁇ (50° C.) 100 111 105
  • Example 85 and Example 86 using the polybutadiene obtained in Example 76 and Example 77 have more excellent tensile stress, impact resilience, abrasion resistance, and low exothermic property than the composition of Comparative Example 9.
  • Example 87 and Example 88 using the polybutadiene obtained in Example 79 and Example 80 have more excellent tensile stress, impact resilience, and low exothermic property than the composition of Comparative Example 9.
  • compositions Example 89 to Example 92 using the polybutadiene obtained in Example 81 to Example 84 have more excellent tensile stress, rebound resilience, abrasion resistance, and low exothermic property than the composition of Comparative Example 9.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 15.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 15.
  • a first compounding, in which SBR, silica, a silane coupling agent, zinc oxide, stearic acid, and an antioxidant were added to UBEPOL-BR 150 L (a conjugated diene polymer obtained by a polymerization using a Co catalyst), manufactured by Ube Industries, Ltd., in a compounding formulation shown in Table 14 in a plastomill, and the mixture was kneaded, was performed.
  • UBEPOL-BR 150 L a conjugated diene polymer obtained by a polymerization using a Co catalyst
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 15.
  • Example 94 Example 10
  • Example 76 30
  • Example 78 30
  • BR150L 30
  • SBR 70 70
  • Silica 65 65
  • Agent Oil 25
  • Zinc oxide 3 3
  • Stearic acid 1
  • Antioxidant 1
  • accelerator 1
  • Vulcanization 2 2
  • Powdery sulfur 1.4
  • 1.4 1.4
  • Example 93 and Example 94 using the polybutadienes obtained in Example 76 and Example 78 have more excellent tensile stress, rebound resilience, abrasion resistance, and low exothermic property than the composition of Comparative Example 10.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 18.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 18.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. The measurement results of various physical properties of the formulation are shown in Table 18.
  • Example Example Comparative 97 98 Example 11 Example 95 50
  • Example 96 50 BR150L 50 Natural 50
  • rubber Carbon black 50
  • Zinc oxide 3 3 3
  • Stearic acid 2
  • Antioxidant 2
  • Aroma oil 3 3 3
  • Vulcanization 1
  • accelerator 1.5 1.5 1.5
  • Example 97 and Example 98 using the modified polybutadienes obtained in Example 95 and Example 96 have more excellent tensile stress, rebound resilience, elongation fatigue resistance, abrasion resistance, and low exothermic property than the composition of Comparative Example 11.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 21.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 21.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 21.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 21.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 21.
  • a first compounding, in which natural rubber, silica, a silane coupling agent, zinc oxide, stearic acid, an antioxidant, and an oil were added to UBEPOL-BR150L (a conjugated diene polymer obtained by a polymerization using a Co catalyst), manufactured by Ube Industries, Ltd., in a compounding formulation shown in Table 20 in a plastomill, and the mixture was kneaded, was performed.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 21.
  • Example 104 to Example 108 using the modified polybutadienes obtained in Example 99 to Example 103 have a larger amount of the filler gel, show a better numeric value in Payne effect showing dispersibility of silica, and have more excellent die swell, tensile stress, rebound resilience, abrasion resistance, and low fuel consumption than the composition of Comparative Example 12.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 24.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 24.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 24.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 24.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation are shown in Table 24.
  • compositions of Example 113 to Example 116 using the cis-1,4-polybutadienes obtained in Example 109 to Example 112 have more excellent tensile stress, rebound resilience, elongation fatigue resistance, abrasion resistance, low exothermic property, and low fuel consumption than the composition of Comparative Example 13.
  • a polymerization was performed at 40° C. for 25 minutes. After 4 ml of an ethanol solution containing an antioxidant was added, the inside pressure of the autoclave was released, and then ethanol was poured into the polymerization solution to recover polybutadiene. Then, the recovered polybutadiene was dried in vacuo at 80° C. for 3 hours. Polymerization results are shown in Table 25.
  • a polymerization was performed at 50° C. for 25 minutes. After 4 ml of an ethanol solution containing an antioxidant was added, the inside pressure of the autoclave was released, and then ethanol was poured into the polymerization solution to recover polybutadiene. Then, the recovered polybutadiene was dried in vacuo at 80° C. for 3 hours. Polymerization results are shown in Table 25.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation were shown in Table 27.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation were shown in Table 27.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation were shown in Table 27.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation were shown in Table 27.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation were shown in Table 27.
  • a second compounding of addition of a vulcanization accelerator and sulfur through a roller was performed to produce a compounded rubber.
  • the compounded rubber was molded according to desired physical properties. Physical properties of a vulcanized product obtained by press-vulcanization at 150° C. were measured. Measurement results of various physical properties of the formulation were shown in Table 27.
  • Example Example Example Compatative 122 123 124 125 126 Example 14 Example 117 50 Example 118 50 Example 119 50 Example 120 50 Example 121 50 BR150L 50 NR 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Aroma Oil 3 3 3 3 3 3 3 3 Stearic acid 2 2 2 2 2 2 2 2 Valcanization 1 1 1 1 1 1 accelerator Powdery sulfur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
  • Example 122 to Example 126 using the cis-1,4-polybutadienes obtained in Example 117 to Example 121 have more excellent tensile stress, rebound resilience, elongation fatigue resistance, low exothermic property, and low fuel consumption than the composition of Comparative Example 14.

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US14/775,961 2013-03-13 2014-03-13 Catalyst for Conjugated Diene Polymerization, Conjugated Diene Polymer and Modified Conjugated Diene Polymer Produced Using the Same, Production Methods Thereof, Rubber Composition for Tire, and Rubber Composition for Rubber Belt Abandoned US20160009835A1 (en)

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