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WO2016039004A1 - Polybutadiène et composition de caoutchouc - Google Patents

Polybutadiène et composition de caoutchouc Download PDF

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Publication number
WO2016039004A1
WO2016039004A1 PCT/JP2015/069791 JP2015069791W WO2016039004A1 WO 2016039004 A1 WO2016039004 A1 WO 2016039004A1 JP 2015069791 W JP2015069791 W JP 2015069791W WO 2016039004 A1 WO2016039004 A1 WO 2016039004A1
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Prior art keywords
polybutadiene
solution
less
added
rubber
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PCT/JP2015/069791
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English (en)
Japanese (ja)
Inventor
斯波　晃司
雄太 山田
駿 深澤
前田　修一
岡本　尚美
Original Assignee
宇部興産株式会社
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Priority to JP2016547755A priority Critical patent/JPWO2016039004A1/ja
Publication of WO2016039004A1 publication Critical patent/WO2016039004A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08C19/02—Hydrogenation
    • 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
    • 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
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to polybutadiene.
  • the present invention also relates to a rubber composition containing this polybutadiene and a tire rubber composition.
  • Polybutadiene has a so-called microstructure that includes a bond portion (1,4-structure) formed by polymerization at the 1,4-position and a bond portion (1,2-structure) formed by polymerization at the 1,2-position. Coexist in the molecular chain.
  • the 1,4-structure is further divided into two types, a cis structure and a trans structure.
  • the 1,2-structure is a structure having a vinyl group as a side chain. It is known that polybutadienes having different microstructures are produced by a polymerization catalyst, and they are used in various applications depending on their properties.
  • polybutadiene having a high molecular linearity that is, having a small degree of branching
  • linearity has excellent characteristics in terms of wear resistance, low heat generation, and rebound resilience.
  • Tcp / ML 1 + 4 which is a ratio of a 5% toluene solution viscosity (Tcp) measured at 25 ° C. and a Mooney viscosity (ML 1 + 4 ) at 100 ° C.
  • Tcp indicates the degree of molecular entanglement in the concentrated solution, and it is considered that the greater the Tcp / ML 1 + 4 , the smaller the degree of branching and the greater the linearity (linearity).
  • polybutadiene having such a large Tcp / ML 1 + 4 and a high molecular linearity (ie, a low degree of branching) exhibits a relatively high cold flow property and a relatively low storage stability. Problems may arise during storage and transport.
  • Patent Documents 1 to 3 describe that a specific compound (modifier) is reacted with a conjugated diene polymer obtained by polymerizing a conjugated diene compound such as polybutadiene (modification). Discloses a method for improving cold flow characteristics (ie, reducing cold flow).
  • Patent Document 4 discloses a modified polybutadiene obtained by modifying a raw material polybutadiene having specific characteristics in the presence of a transition metal catalyst as a polybutadiene having improved cold flow characteristics.
  • silica is used as a polymer composition such as polybutadiene that does not require a modification step and can be manufactured at low cost and has improved cold flow resistance (that is, cold flow is suppressed).
  • a polymer composition is disclosed that is dispersed in a polymer (existing in a highly dispersed state) at a content of more than 0 part by weight and not more than 5 parts by weight with respect to 100 parts by weight of the polymer.
  • An object of the present invention is to provide a polybutadiene having a comparatively large Tcp / ML 1 + 4 which is an index of molecular linearity (linearity) and excellent in cold flow characteristics.
  • Another object of the present invention is to provide a polybutadiene having excellent properties possessed by a polybutadiene having a low degree of branching, for example, excellent wear resistance, low heat build-up, rebound resilience, and excellent cold flow properties. To do.
  • the present invention relates to the following matters.
  • the ratio (Tcp / ML 1 + 4 ) of 5% toluene solution viscosity (Tcp) measured at 25 ° C. and Mooney viscosity (ML 1 + 4 ) at 100 ° C. is 1.3 or more and 5.0 or less,
  • the molecular weight distribution (Mw / Mn) is 2.0 or more and less than 4,
  • the polybutadiene according to item 1, wherein the Mooney viscosity (ML 1 + 4 ) at 100 ° C. is 25 or more and 60 or less.
  • CF cold flow rate
  • Item 6 The polybutadiene according to any one of Items 1 to 5, wherein the cis-1,4-structure content is 90% or more.
  • a rubber composition comprising the polybutadiene according to any one of items 1 to 6. 8).
  • a tire rubber composition comprising the polybutadiene according to any one of items 1 to 6. 9.
  • Item 11 The tire rubber composition according to Item 9 or 10, wherein the rubber reinforcing agent is carbon black and / or silica. 12 12.
  • a tire comprising the rubber composition for tire according to any one of items 8 to 11 as a rubber base material.
  • a polybutadiene having excellent properties of a polybutadiene having a low degree of branching for example, excellent wear resistance, low heat generation, rebound resilience, and excellent cold flow properties. It can.
  • the polybutadiene of the present invention is excellent in wear resistance, low heat build-up, rebound resilience, and the like, and is also excellent in cold flow characteristics, so that it can be suitably used for rubber compositions, particularly tire rubber compositions.
  • the polybutadiene of the first aspect of the present invention is The ratio (Tcp / ML 1 + 4 ) of 5% toluene solution viscosity (Tcp) measured at 25 ° C. and Mooney viscosity (ML 1 + 4 ) at 100 ° C. is 1.3 or more and 5.0 or less, The molecular weight distribution (Mw / Mn) is 2.0 or more and less than 4, The cold flow rate (CF) is 5.5 mg / min or less.
  • Tcp / ML 1 + 4 which is a ratio of 5% toluene solution viscosity (Tcp) measured at 25 ° C. and Mooney viscosity (ML 1 + 4 ) at 100 ° C., is conventionally used as an index of linearity. It is considered that the larger / ML 1 + 4, the smaller the degree of branching and the greater the linearity (linearity).
  • the polybutadiene of the first aspect of the present invention is an unmodified unmodified polybutadiene, but has a relatively large Tcp / ML 1 + 4 of 1.3 or more and a cold flow rate (CF) of 5.5 mg / min. The following is small. Such a polybutadiene has not existed in the past, and can be obtained by performing polymerization using a specific catalyst, as will be described later.
  • Tcp / ML 1 + 4 of the polybutadiene according to the first aspect of the present invention is 1.3 or more, preferably 1.5 or more, and particularly preferably 1.7 or more. Further, Tcp / ML 1 + 4 of the polybutadiene of the first aspect of the present invention is 5.0 or less, preferably 4.0 or less, more preferably 3.5 or less, and particularly preferably 3.0. It is as follows.
  • the cold flow rate (CF) of the polybutadiene of the first aspect of the present invention is 5.5 mg / min or less, preferably 5.0 mg / min or less, more preferably 4.8 mg / min or less, Especially preferably, it is 4.6 mg / min or less.
  • the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), of the polybutadiene of the first aspect of the present invention is 2.0 or more, preferably 2.3 or more. Yes, particularly preferably 2.5 or more. Further, the molecular weight distribution (Mw / Mn) of the polybutadiene of the first aspect of the present invention is less than 4, preferably 3.8 or less, more preferably 3.5 or less, and particularly preferably 3. 2 or less.
  • the polybutadiene of the first aspect of the present invention satisfying the physical property values as described above has excellent properties such as wear resistance, low heat build-up, and rebound resilience, and also has excellent cold flow properties, that is, storage (storage). Excellent stability.
  • the Mooney viscosity (ML 1 + 4 ) at 100 ° C. of the polybutadiene of the first aspect of the present invention is preferably 25 or more and 60 or less.
  • the ML 1 + 4 of the polybutadiene of the first aspect of the present invention is more preferably 30 or more, and particularly preferably 35 or more.
  • ML 1 + 4 of the polybutadiene of the first aspect of the present invention is more preferably 57 or less, and particularly preferably 55 or less.
  • the number average molecular weight (Mn) of the polybutadiene according to the first aspect of the present invention is not particularly limited, but is preferably 50,000 or more and 300,000 or less, more preferably 100,000 or more and 250,000 or less.
  • the weight average molecular weight (Mw) of the polybutadiene of the first aspect of the present invention is not particularly limited, but is preferably 300000 or more and 700000 or less, more preferably 350,000 or more and 600000 or less.
  • the polybutadiene of the first aspect of the present invention preferably has a cis-1,4-structure content of 90% or more.
  • the cis-1,4-structure content of the polybutadiene according to the first aspect of the present invention is more preferably 92% or more, more preferably 93% or more, still more preferably 94% or more, and further preferably 94.5% or more. Particularly preferred is 95% or more or more than 95%.
  • the intrinsic viscosity (intrinsic viscosity measured at 25 ° C. in toluene) [ ⁇ ] of the polybutadiene according to the first aspect of the present invention is not particularly limited, but is preferably 0.1 to 10, more preferably 1 to 7. Particularly preferably, it can be controlled to 1.2 to 5.
  • the polybutadiene of the first aspect of the present invention may be a copolymer, and in addition to the butadiene monomer, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, Conjugated dienes such as 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Acyclic monoolefins such as 1-octene, cyclic monoolefins such as cyclopentene, cyclohexene and norbornene, and / or aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, dicyclopentadiene, 5-ethylidene-2-norbornene, Other monomers such as non-con
  • the polybutadiene of the first aspect of the present invention has excellent characteristics and is excellent in storage (storage) stability, and therefore can be suitably used for various applications, for example, rubber applications, particularly tires. It can be suitably used for a rubber composition.
  • the rubber composition for tires containing the polybutadiene of the first aspect of the present invention can be suitably used particularly for low fuel consumption tires.
  • the rubber composition containing the polybutadiene of the first aspect of the present invention can be suitably used for rubber belts, rubber crawlers, golf balls, footwear, fenders and the like.
  • the polybutadiene of the second aspect of the present invention is The number of long chain branch points per 10,000 butadiene monomer units determined from 13 C-NMR measurement of hydrogenated polybutadiene (provided that the long chain branch points are formed from two or more butadiene units).
  • Y (50%) / Y (10%) is an index of molecular linearity (linearity).
  • linearity the difference between Y (50%) and Y (10%) is small, that is, Y (50%) / Y (10%) is close to 1, and the degree of branching is large. If linearity is low, Y (50%) / Y (10%) increases.
  • Y (50%) / Y (10%) is larger than 2, while the number of long chain branching points is 9 or less and small.
  • Such a polybutadiene has not existed in the past, and can be obtained by performing polymerization using a specific catalyst, as will be described later.
  • the polybutadiene according to the second aspect of the present invention that satisfies the physical property values as described above has excellent properties such as wear resistance, low heat build-up, and rebound resilience, and also has excellent cold flow properties, that is, storage ( Storage) Excellent stability.
  • the number of long-chain branch points per 10,000 butadiene monomer units determined from 13 C-NMR measurement of the polybutadiene of the second aspect of the present invention is 9 or less, preferably 8 or less. Further, the number of long chain branch points per 10,000 butadiene monomer units determined from 13 C-NMR measurement of the polybutadiene of the second aspect of the present invention is not particularly limited, but is preferably 2 or more. The method for obtaining the number of long chain branch points will be specifically described in Examples.
  • Concentration-converted G ′′ obtained from measurement of the angular frequency dependence of the storage elastic modulus G ′ and loss elastic modulus G ′′ of the liquid paraffin 50% by mass and 10% by mass solution of polybutadiene of the second aspect of the present invention.
  • Y (50%) / Y (10%) of the polybutadiene of the second aspect of the present invention is not particularly limited, but is preferably 4.5 or less, more preferably 4.0 or less, particularly Preferably it is 3.8 or less.
  • the method for obtaining Y (50%) / Y (10%) will be specifically described in the examples.
  • the cold flow rate (CF) of the polybutadiene of the second aspect of the present invention is not particularly limited, but is preferably 5.5 mg / min or less, more preferably 5.0 mg / min or less, more preferably 4 0.8 mg / min or less, particularly preferably 4.6 mg / min or less.
  • the number average molecular weight (Mn) of the polybutadiene of the second aspect of the present invention is not particularly limited, but is preferably 50,000 or more and 300,000 or less, more preferably 100,000 or more and 250,000 or less.
  • the weight average molecular weight (Mw) of the polybutadiene of the second aspect of the present invention is not particularly limited, but is preferably 300000 or more and 700000 or less, more preferably 350,000 or more and 600000 or less.
  • the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of the polybutadiene of the second aspect of the present invention is preferably 2.0 or more, more preferably 2. 3 or more, particularly preferably 2.5 or more.
  • the molecular weight distribution (Mw / Mn) of the polybutadiene according to the second aspect of the present invention is preferably less than 4, more preferably 3.8 or less, more preferably 3.5 or less, particularly preferably. Is 3.2 or less.
  • the Mooney viscosity (ML 1 + 4 ) at 100 ° C. of the polybutadiene of the second aspect of the present invention is preferably 25 or more and 60 or less.
  • the ML 1 + 4 of the polybutadiene of the second aspect of the present invention is more preferably 30 or more, and particularly preferably 35 or more.
  • ML 1 + 4 of the polybutadiene of the second aspect of the present invention is more preferably 57 or less, and particularly preferably 55 or less.
  • Tcp / ML 1 + 4 of the polybutadiene of the second aspect of the present invention is preferably 1.3 or more, more preferably 1.5 or more, and particularly preferably 1.7 or more. Further, Tcp / ML 1 + 4 of the polybutadiene of the second aspect of the present invention is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, and particularly preferably 3.0 or less.
  • the polybutadiene of the second aspect of the present invention preferably has a cis-1,4-structure content of 90% or more.
  • the cis-1,4-structure content of the polybutadiene according to the second aspect of the present invention is more preferably 92% or more, more preferably 93% or more, still more preferably 94% or more, and further preferably 94.5% or more. Particularly preferred is 95% or more or more than 95%.
  • the intrinsic viscosity (intrinsic viscosity measured at 25 ° C. in toluene) [ ⁇ ] of the polybutadiene according to the second aspect of the present invention is not particularly limited, but is preferably 0.1 to 10, more preferably 1 to 7. Particularly preferably, it can be controlled to 1.2 to 5.
  • the polybutadiene of the second aspect of the present invention may be a copolymer, and in addition to the butadiene monomer, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, Conjugated dienes such as 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Acyclic monoolefins such as 1-octene, cyclic monoolefins such as cyclopentene, cyclohexene and norbornene, and / or aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, dicyclopentadiene, 5-ethylidene-2-norbornene, Other monomers such as non-con
  • the polybutadiene of the second aspect of the present invention has excellent characteristics and is excellent in storage (storage) stability, and therefore can be suitably used for various applications, such as rubber applications, particularly tires. It can be suitably used for a rubber composition.
  • the rubber composition for tires containing the polybutadiene of the second aspect of the present invention can be suitably used particularly for low fuel consumption tires.
  • the rubber composition containing the polybutadiene of the second aspect of the present invention can be suitably used for rubber belts, rubber crawlers, golf balls, footwear, fenders and the like.
  • the polybutadiene of the third aspect of the present invention is The number of long chain branch points per 10,000 butadiene monomer units determined from 13 C-NMR measurement of hydrogenated polybutadiene (provided that the long chain branch points are formed from two or more butadiene units). Is a branch point where a branched chain having 6 or more carbon atoms is bonded to the main chain.) Is 9 or less, The cold flow rate (CF) is 5.5 mg / min or less.
  • Tcp / ML 1 + 4 which is a ratio of 5% toluene solution viscosity (Tcp) measured at 25 ° C. and Mooney viscosity (ML 1 + 4 ) at 100 ° C., as an index of molecular linearity (linearity).
  • polybutadiene which has a large Tcp / ML 1 + 4 , that is, a low degree of branching and high linearity, tended to exhibit a relatively high cold flow.
  • the polybutadiene of the third aspect of the present invention has a small number of long-chain branching points of 9 or less and a cold flow rate (CF) as small as 5.5 mg / min or less.
  • CF cold flow rate
  • the polybutadiene according to the third aspect of the present invention satisfying the physical property values as described above has excellent properties such as wear resistance, low heat build-up, and rebound resilience, and also has excellent cold flow properties, that is, storage ( Storage) Excellent stability.
  • the number of long-chain branch points per 10,000 butadiene monomer units determined from 13 C-NMR measurement of the polybutadiene of the third aspect of the present invention is 9 or less, preferably 8 or less. Further, the number of long chain branch points per 10,000 butadiene monomer units determined from 13 C-NMR measurement of the polybutadiene of the third aspect of the present invention is not particularly limited, but is preferably 2 or more.
  • the cold flow rate (CF) of the polybutadiene of the third aspect of the present invention is 5.5 mg / min or less, preferably 5.0 mg / min or less, more preferably 4.8 mg / min or less, Especially preferably, it is 4.6 mg / min or less.
  • the number average molecular weight (Mn) of the polybutadiene of the third aspect of the present invention is not particularly limited, but is preferably 50,000 or more and 300,000 or less, more preferably 100,000 or more and 250,000 or less.
  • Mw weight average molecular weight of the polybutadiene of the 3rd aspect of this invention is not specifically limited, Preferably it is 300000-700000, More preferably, it is 350,000-600000.
  • the molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polybutadiene of the third aspect of the present invention is preferably 2.0 or more, more preferably 2. 3 or more, particularly preferably 2.5 or more. Further, the molecular weight distribution (Mw / Mn) of the polybutadiene of the third aspect of the present invention is preferably less than 4, more preferably 3.8 or less, more preferably 3.5 or less, particularly preferably. Is 3.2 or less.
  • the Mooney viscosity (ML 1 + 4 ) at 100 ° C. of the polybutadiene of the third aspect of the present invention is preferably 25 or more and 60 or less.
  • the ML 1 + 4 of the polybutadiene of the third aspect of the present invention is more preferably 30 or more, and particularly preferably 35 or more.
  • ML 1 + 4 of the polybutadiene of the third aspect of the present invention is more preferably 57 or less, and particularly preferably 55 or less.
  • Tcp / ML 1 + 4 of the polybutadiene according to the third aspect of the present invention is preferably 1.3 or more, more preferably 1.5 or more, and particularly preferably 1.7 or more. Further, Tcp / ML 1 + 4 of the polybutadiene of the third aspect of the present invention is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, particularly preferably. 3.0 or less.
  • the polybutadiene of the third aspect of the present invention preferably has a cis-1,4-structure content of 90% or more.
  • the cis-1,4-structure content of the polybutadiene of the third aspect of the present invention is more preferably 92% or more, more preferably 93% or more, still more preferably 94% or more, and further preferably 94.5% or more. Particularly preferred is 95% or more or more than 95%.
  • the intrinsic viscosity (intrinsic viscosity measured in toluene at 25 ° C.) [ ⁇ ] of the third aspect of the present invention is not particularly limited, but is preferably 0.1 to 10, more preferably 1 to 7. Particularly preferably, it can be controlled to 1.2 to 5.
  • the polybutadiene of the third aspect of the present invention may be a copolymer, and in addition to the butadiene monomer, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, Conjugated dienes such as 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Acyclic monoolefins such as 1-octene, cyclic monoolefins such as cyclopentene, cyclohexene and norbornene, and / or aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, dicyclopentadiene, 5-ethylidene-2-norbornene, Other monomers such as non-con
  • the polybutadiene of the third aspect of the present invention has excellent characteristics and is excellent in storage (storage) stability, and therefore can be suitably used for various applications, for example, rubber applications, particularly tires. It can be suitably used for a rubber composition.
  • the rubber composition for tires containing the polybutadiene of the third aspect of the present invention can be suitably used particularly for low fuel consumption tires.
  • the rubber composition containing the polybutadiene of the third aspect of the present invention can be suitably used for rubber belts, rubber crawlers, golf balls, footwear, fenders and the like.
  • the polybutadiene of the fourth aspect of the present invention is The ratio (Tcp / ML 1 + 4 ) of 5% toluene solution viscosity (Tcp) measured at 25 ° C. to Mooney viscosity (ML 1 + 4 ) at 100 ° C.
  • Y (50%) / Y (10%) is an index of molecular linearity (linearity).
  • linearity the difference between Y (50%) and Y (10%) is small, that is, Y (50%) / Y (10%) is close to 1, and the degree of branching is large. If linearity is low, Y (50%) / Y (10%) increases.
  • Tcp 5% toluene solution viscosity measured at 25 ° C. to the Mooney viscosity (ML 1 + 4 ) at 100 ° C.
  • ML 1 + 4 Mooney viscosity
  • the polybutadiene of the fourth aspect of the present invention has a high Tcp / ML 1 + 4 of 1.3 or more (that is, a low degree of branching and high linearity), while Y (50%) / Y (10%) Is greater than 2 (ie, indicates a high degree of branching and low linearity).
  • a polybutadiene has not existed in the past, and can be obtained by performing polymerization using a specific catalyst, as will be described later.
  • the polybutadiene according to the fourth aspect of the present invention satisfying the physical property values as described above has excellent properties such as abrasion resistance, low heat build-up, and rebound resilience, and also has excellent cold flow properties, that is, storage ( Storage) Excellent stability.
  • the Tcp / ML 1 + 4 of the polybutadiene according to the fourth aspect of the present invention is 1.3 or more, preferably 1.5 or more, and particularly preferably 1.7 or more.
  • the Tcp / ML 1 + 4 of the polybutadiene of the fourth aspect of the present invention is preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, and particularly preferably 3.0 or less.
  • Concentration-converted G ′′ obtained from measurement of the angular frequency dependence of the storage elastic modulus G ′ and loss elastic modulus G ′′ of the liquid paraffin 50% by mass and 10% by mass solution of polybutadiene of the fourth aspect of the present invention.
  • Y (50%) / Y (10%) of the polybutadiene of the fourth aspect of the present invention is not particularly limited, but is preferably 4.5 or less, more preferably 4.0 or less, particularly Preferably it is 3.8 or less.
  • the cold flow rate (CF) of the polybutadiene of the fourth aspect of the present invention is not particularly limited, but is preferably 5.5 mg / min or less, more preferably 5.0 mg / min or less, more preferably 4 0.8 mg / min or less, particularly preferably 4.6 mg / min or less.
  • the number average molecular weight (Mn) of the polybutadiene according to the fourth aspect of the present invention is not particularly limited, but is preferably 50,000 or more and 300,000 or less, more preferably 100,000 or more and 250,000 or less.
  • the weight average molecular weight (Mw) of the polybutadiene of the 4th aspect of this invention is not specifically limited, Preferably it is 300000 or more and 700000 or less, More preferably, it is 350,000 or more and 600000 or less.
  • the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), of the polybutadiene of the fourth aspect of the present invention is preferably 2.0 or more, more preferably 2. 3 or more, particularly preferably 2.5 or more.
  • the molecular weight distribution (Mw / Mn) of the polybutadiene according to the fourth aspect of the present invention is preferably less than 4, more preferably 3.8 or less, more preferably 3.5 or less, particularly preferably. Is 3.2 or less.
  • the Mooney viscosity (ML 1 + 4 ) at 100 ° C. of the polybutadiene of the fourth aspect of the present invention is preferably 25 or more and 60 or less.
  • the ML 1 + 4 of the polybutadiene of the fourth aspect of the present invention is more preferably 30 or more, and particularly preferably 35 or more.
  • ML 1 + 4 of the polybutadiene of the fourth aspect of the present invention is more preferably 57 or less, and particularly preferably 55 or less.
  • the polybutadiene of the fourth aspect of the present invention preferably has a cis-1,4-structure content of 90% or more.
  • the cis-1,4-structure content of the polybutadiene according to the fourth aspect of the present invention is more preferably 92% or more, more preferably 93% or more, still more preferably 94% or more, and further preferably 94.5% or more. Particularly preferred is 95% or more or more than 95%.
  • the intrinsic viscosity (intrinsic viscosity measured at 25 ° C. in toluene) [ ⁇ ] of the polybutadiene according to the fourth aspect of the present invention is not particularly limited, but is preferably 0.1 to 10, more preferably 1 to 7. Particularly preferably, it can be controlled to 1.2 to 5.
  • the polybutadiene of the fourth aspect of the present invention may be a copolymer, and in addition to the butadiene monomer, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, Conjugated dienes such as 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Acyclic monoolefins such as 1-octene, cyclic monoolefins such as cyclopentene, cyclohexene and norbornene, and / or aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, dicyclopentadiene, 5-ethylidene-2-norbornene, Other monomers such as non-con
  • the polybutadiene of the fourth aspect of the present invention has excellent characteristics and is excellent in storage (storage) stability, and therefore can be suitably used for various applications, for example, rubber applications, particularly tires. It can be suitably used for a rubber composition.
  • the rubber composition for tires containing the polybutadiene of the fourth aspect of the present invention can be suitably used particularly for low fuel consumption tires.
  • the rubber composition containing the polybutadiene of the fourth aspect of the present invention can be suitably used for rubber belts, rubber crawlers, golf balls, footwear, fenders, and the like.
  • polybutadiene of the present invention can be produced, for example, as follows.
  • the polybutadiene of the present invention is not limited to those produced by the following production method.
  • An organometallic compound (C) of an element selected from Group 2, Group 12, and Group 13 is preferably used.
  • R 1 , R 2 and R 3 each represent hydrogen or a substituent having 1 to 12 carbon atoms.
  • O represents an oxygen atom
  • M represents Gd (gadolinium atom), Tb (terbium atom), Dy ( Dysprosium atom), Ho (holmium atom), Er (erbium atom), or Tm (thulium atom).
  • substituent having 1 to 12 carbon atoms in R 1 to R 3 of the general formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, Isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, saturated hydrocarbon group such as dodecyl group, unsaturated hydrocarbon group such as vinyl group, 1-propenyl group, and allyl group, cyclohexyl Group, alicyclic hydrocarbon group such as methylcyclohexyl group, and ethylcyclohexyl group,
  • aromatic hydrocarbon groups Furthermore, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at an arbitrary position are also included. Of these, a saturated hydrocarbon group having 1 to 12 carbon atoms is preferable, and a saturated hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.
  • R 1 to R 3 in the general formula (1) are as follows:
  • R 2 is hydrogen or a substituent having 1 to 12 carbon atoms (preferably a saturated hydrocarbon group), and R 1 and R 3 are substituents having 1 to 12 carbon atoms ( A saturated hydrocarbon group is preferred.
  • R 2 is hydrogen or a substituent having 1 to 6 carbon atoms (preferably a saturated hydrocarbon group), and R 1 and R 3 are each a substituent having 1 to 6 carbon atoms (preferably a saturated hydrocarbon group).
  • R 2 is hydrogen or a substituent having 1 to 6 carbon atoms (preferably a saturated hydrocarbon group)
  • R 1 and R 3 are each a substituent having 1 to 6 carbon atoms (preferably a saturated hydrocarbon group).
  • nonmetallocene metal compound (A) of the general formula (1) in which M is Gd (gadolinium atom) 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- Pentandionato) gadolinium, tris (2,4-hexanedionate) gadolinium, tris (1,5-dicyclopentyl-2,4-pentandionato) gadolinium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) gadolinium and the like.
  • tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium tris (2,6-dimethyl-3,5-heptanedionato) gadolinium, tris (2,4-pentanedioated) Nato) gadolinium and the like.
  • tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium and tris (2,6-dimethyl-3,5-heptanedionato) gadolinium.
  • nonmetallocene metal compound (A) of the general formula (1) in which M is Tb (terbium atom) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium, Tris (2,6,6-trimethyl-3,5-heptanedionato) terbium, Tris (2,6-dimethyl-3,5-heptanedionato) terbium, Tris (3,5-heptanedionato) terbium, Tris (2,4- Pentandionato) terbium, tris (2,4-hexanedionate) terbium, tris (1,5-dicyclopentyl-2,4-pentandionato) terbium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) terbium and the like.
  • nonmetallocene-type metal compound (A) of the general formula (1) in which M is Dy include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium, Tris (2,6,6-trimethyl-3,5-heptanedionato) dysprosium, Tris (2,6-dimethyl-3,5-heptaneedionato) dysprosium, Tris (3,5-heptaneedionato) dysprosium, Tris (2,4- Pentanedionate) dysprosium, tris (2,4-hexanedionato) dysprosium, tris (1,5-dicyclopentyl-2,4-pentanedionato) dysprosium, tris (1,5-dicyclohexyl-2,4-pentane And diatoprosium).
  • tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium tris (2,6-dimethyl-3,5-heptaneedionato) dysprosium, tris (2,4-pentanedioe) Nato) dysprosium.
  • tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium and tris (2,6-dimethyl-3,5-heptanedionato) dysprosium.
  • nonmetallocene metal compound (A) of the general formula (1) in which M is Ho (holmium atom) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium, Tris (2,6,6-trimethyl-3,5-heptanedionato) holmium, Tris (2,6-dimethyl-3,5-heptanedionato) holmium, Tris (3,5-heptanedionato) holmium, Tris (2,4- Pentandionato) holmium, Tris (2,4-hexanedionate) holmium, Tris (1,5-dicyclopentyl-2,4-pentandionato) holmium, Tris (1,5-dicyclohexyl-2,4-pentane) And diato) holmium.
  • tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium tris (2,6-dimethyl-3,5-heptanedionato) holmium, tris (2,4-pentanedioated) Nato) holmium and the like.
  • nonmetallocene metal compound (A) of the general formula (1) in which M is Er (erbium atom) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium, Tris (2,6,6-trimethyl-3,5-heptanedionato) erbium, Tris (2,6-dimethyl-3,5-heptanedionato) erbium, Tris (3,5-heptanedionato) erbium, Tris (2,4- Pentandionato) erbium, Tris (2,4-hexanedionate) erbium, Tris (1,5-dicyclopentyl-2,4-pentandionato) erbium, Tris (1,5-dicyclohexyl-2,4-pentane (Dionato) Erbium.
  • nonmetallocene-type metal compound (A) of the general formula (1) in which M is Tm (thulium atom) include tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium, Tris (2,6,6-trimethyl-3,5-heptanedionato) thulium, Tris (2,6-dimethyl-3,5-heptaneedionato) thulium, Tris (3,5-heptaneedionato) thulium, Tris (2,4- Pentandionato) thulium, tris (2,4-hexanedionate) thulium, tris (1,5-dicyclopentyl-2,4-pentanedionato) thulium, tris (1,5-dicyclohexyl-2,4-pentane) (Dionato) thulium and the like.
  • tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium and tris (2,6-dimethyl-3,5-heptaneedionato) thulium are particularly preferred.
  • the nonmetallocene metal compound (A) may be used alone or in combination of two or more.
  • examples of the non-coordinating anion include tetra (phenyl) borate, tetra (fluorophenyl) borate, and tetrakis (difluorophenyl).
  • examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation.
  • the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri-substituted phenylcarbonium cation.
  • the tri-substituted phenylcarbonium cation include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.
  • ammonium cation examples include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tri (n-butyl) ammonium cations, tri (i-butyl) ammonium cations, and the like, N, N-dimethyl N, N-dialkylanilinium cations such as anilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. And dialkylammonium cations.
  • phosphonium cations include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (dimethylphenyl) phosphonium cation, etc.
  • arylphosphonium cations include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, etc.
  • arylphosphonium cations include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, etc.
  • ionic compound (B) those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.
  • a boron-containing compound is preferable, and among them, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (fluorophenyl) borate, N, N-dimethylaniline are particularly preferable. Nitrotetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferable.
  • An ionic compound (B) may be used independently and may be used in combination of 2 or more type.
  • alumoxane (aluminoxane) may be used in place of the ionic compound composed of the non-coordinating anion and cation as component (B).
  • the alumoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and has a general formula (—Al (R ′) O—) n (R ′ is a hydrocarbon group having 1 to 10 carbon atoms). Including a partly substituted with a halogen atom and / or an alkoxy group, where n is the degree of polymerization, and is 5 or more, preferably 10 or more). .
  • R ′ examples include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is preferable.
  • organoaluminum compound used as a raw material for alumoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. Among these, alumoxane using a mixture of trimethylaluminum and triisobutylaluminum as a raw material can be suitably used.
  • Typical examples of the condensing agent used in the production of alumoxane include water, but other than that, any of the above-described organoaluminum compounds that undergo a condensation reaction, for example, adsorbed water such as inorganic substances, diols, and the like.
  • organometallic compound of an element selected from Group 2, Group 12 and Group 13 of the periodic table as the component (C) for example, organic magnesium, organic zinc, organic aluminum, and the like are used.
  • organic magnesium, organic zinc, organic aluminum, and the like are used.
  • Organic aluminum halogen compounds such as alkylaluminum dichloride; organoaluminum hydride compounds such as dialkylaluminum hydride.
  • 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. Can be mentioned.
  • dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, ethyl hexyl magnesium and the like can be mentioned.
  • dialkyl zinc such as dimethyl zinc, diethyl zinc, diisobutyl zinc, dihexyl zinc, dioctyl zinc, didecyl zinc and the like can be mentioned.
  • trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum.
  • dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride
  • organoaluminum halogen compounds such as ethylaluminum sesquichloride and ethylaluminum dichloride
  • hydrogenated organoaluminum compounds such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum sesquihydride.
  • organometallic compounds (C) of elements selected from Groups 2, 12, and 13 of the periodic table can be used alone or in combination of two or more.
  • an organometallic compound of a group 13 element is preferable, among which organic aluminum is preferable, and examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Particularly preferred is triethylaluminum.
  • Component (A) nonmetallocene-type metal compound
  • component (B) ionic compound comprising non-coordinating anion and cation
  • component (C) second periodic table of the polybutadiene polymerization catalyst of the present invention
  • the ratio of the organometallic compound of an element selected from Group 12, Group 12 and Group 13) is not particularly limited, but the amount of component (B) is 0.5 to 10 moles per mole of component (A) 1 to 5 mol is particularly preferable.
  • the amount of component (C) is preferably 10 to 10,000 moles, and particularly preferably 50 to 7000 moles per mole of component (A).
  • polymerization can be carried out using a catalyst comprising the above-mentioned components (A), (B) and (C), but the polybutadiene obtained is within the range not impeding the effects of the present invention other than the above.
  • the molecular weight regulator and the like can be added.
  • a compound selected from hydrogen, a metal hydride compound, and a hydrogenated organometallic compound can be used as the molecular weight regulator.
  • Metal hydride compounds 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.
  • hydrogenated organometallic compounds include alkylboranes such as methylborane, ethylborane, propylborane, butylborane, and phenylborane; dialkylboranes such as dimethylborane, diethylborane, dipropylborane, dibutylborane, and diphenylborane; methylaluminum dihydride Alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride, butyl aluminum dihydride, phenyl aluminum dihydride; dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, Diphenyl aluminum hydra Dialkyl aluminum hydrides such as methyl silane, ethyl silane, propyl silane, butyl silane, phenyl silane, dimethyl silane
  • diisobutylaluminum hydride and diethylaluminum hydride are preferable.
  • each catalyst component can be supported on an inorganic compound or an organic polymer compound.
  • the order of addition of the above catalyst components is not particularly limited, and can be performed, for example, in the following order.
  • component (A) in the presence or absence of monomers in an inert organic solvent, add component (C) and the molecular weight regulator described above in any order, and then add component (B). Added.
  • the component (C) is added in the presence or absence of the monomer, the component (A) and the component (B) are added in an arbitrary order, and then the molecular weight regulator described above is added. Added.
  • the monomer added first may be the total amount of the monomer or a part thereof.
  • the polybutadiene of the present invention may be copolymerized using a small amount of other monomers in addition to 1,3-butadiene.
  • monomers other than 1,3-butadiene as raw materials include isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2 Conjugated dienes such as 1,4-hexadiene, acyclic monoolefins such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, cyclopentene , Cyclic monoolefins such as cyclohexene and norbornene, and / or aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, non-conjugated
  • the polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) or solution polymerization using a monomer such as 1,3-butadiene as a polymerization solvent can be applied.
  • Solvents for solution polymerization include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene, Examples thereof include olefinic hydrocarbons such as the above olefin compounds and cis-2-butene and trans-2-butene.
  • benzene, toluene, xylene, cyclohexane, or cis-2-butene and trans-2-butene. And the like are preferably used.
  • These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polymerization temperature is preferably in the range of ⁇ 30 to 150 ° C., more preferably in the range of 0 to 100 ° C., and particularly preferably in the range of 10 to 80 ° C.
  • the polymerization time is preferably 1 minute to 12 hours, more preferably 3 minutes to 5 hours, particularly preferably 5 minutes to 1 hour.
  • the amount of the polybutadiene polymerization catalyst of the present invention is not particularly limited, but the concentration of the component (A) (metal compound) is preferably 1 to 100 ⁇ mol / L, and preferably 2 to 50 ⁇ mol / L. It is particularly preferred.
  • the inside of the polymerization tank is released as necessary, and post-treatment such as washing and drying steps is performed.
  • the polybutadiene of the present invention can be obtained.
  • M is Gd (gadolinium atom).
  • the resulting polybutadiene can be removed.
  • the polybutadiene of the present invention can be suitably used for, for example, a rubber composition, particularly a tire rubber composition.
  • the rubber composition of the present invention is characterized by containing one or more of the polybutadienes of the present invention.
  • the polybutadiene of the present invention is blended alone or blended with other synthetic rubber or natural rubber, and if necessary, is oil-extended with process oil, and then a filler such as carbon black, a vulcanizing agent.
  • a filler such as carbon black
  • Vulcanization accelerators and other ordinary compounding agents can be added to vulcanize the tires, hoses, belts, and other industrial products that require mechanical properties and wear resistance. it can. It can also be used as a plastic material modifier, for example, a high impact polystyrene modifier.
  • the tire rubber composition of the present invention comprises one or more of the polybutadienes of the present invention, the polybutadiene of the present invention (hereinafter referred to as “polybutadiene ( ⁇ )”), and a diene polymer other than polybutadiene. (Hereinafter referred to as “diene polymer ( ⁇ )”) and a rubber reinforcing agent (hereinafter referred to as “rubber reinforcing agent ( ⁇ )”).
  • the tire rubber composition includes a polybutadiene ( ⁇ ), a rubber component ( ⁇ ) + ( ⁇ ) composed of a diene polymer ( ⁇ ) other than ( ⁇ ), and a rubber reinforcing agent ( ⁇ ).
  • the rubber reinforcing agent ( ⁇ ) is preferably contained in an amount of 30 to 80 parts by mass with respect to 100 parts by mass of the rubber component ( ⁇ ) + ( ⁇ ). That is, the blending amount of the rubber reinforcing agent ( ⁇ ) is preferably based on 100 parts by mass of the rubber component ( ⁇ ) + ( ⁇ ) composed of polybutadiene ( ⁇ ) and a diene polymer ( ⁇ ) other than ( ⁇ ). Is 30 to 80 parts by mass, more preferably 40 to 70 parts by mass.
  • the mass ratio of the rubber component ( ⁇ ) + ( ⁇ ) of the tire rubber composition is 90 to 5 parts by mass of polybutadiene ( ⁇ ) and 10 to 95 parts by mass of a diene polymer ( ⁇ ) other than polybutadiene ( ⁇ ). It is preferable that
  • the diene polymer ( ⁇ ) other than polybutadiene used in the rubber composition for tires of the present invention is preferably a vulcanizable rubber.
  • natural rubber 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 Examples thereof include butadiene rubber.
  • the diene polymer ( ⁇ ) is preferably at least one of natural rubber, styrene-butadiene rubber, and polyisoprene. These rubbers may be used alone or in combination of two or more.
  • Examples of the rubber reinforcing agent ( ⁇ ) used in the tire rubber composition of the present invention include various types of carbon black, silica, activated calcium carbonate, ultrafine magnesium silicate, talc, mica and the like.
  • the rubber reinforcing agent ( ⁇ ) of the tire rubber composition is preferably at least one of carbon black and silica.
  • the rubber reinforcing agent may be used alone or in combination of two or more.
  • a silane coupling agent can be used as an additive.
  • the silane coupling agent used as an additive is an organosilicon compound represented by the general formula R 7 n SiR 8 4-n , where R 7 is a vinyl group, acyl group, allyl group, allyloxy group, amino group, epoxy group, An organic group having 1 to 20 carbon atoms having a reactive group selected from a mercapto group, a chloro group, an alkyl group, a phenyl group, hydrogen, a styryl group, a methacryl group, an acrylic group, a ureido group, and the like; R 8 is a chloro group , An alkoxy group, an acetoxy group, an isopropenoxy group, an amino group, and the like, and n represents an integer of 1 to 3.
  • the R 7 of the above silane coupling agent those containing a vinyl group and / or a chloro
  • the addition amount of the additive silane coupling agent is preferably 0.2 to 20 parts by mass, more preferably 3 to 15 parts by mass, and particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the filler. If it is less than the above range, it may cause scorching. Moreover, when more than said range, it may become a cause of a deterioration of a tensile characteristic and elongation.
  • Fullerenes as disclosed in JP-A-2006-131819 may be used as the rubber reinforcing agent ( ⁇ ) blended in the tire rubber composition.
  • Examples of fullerenes include C60, C70, a mixture of C60 and C70, and derivatives thereof.
  • Fullerene derivatives include PCBM (Phenyl C61-butylic acid methylester), PCBNB (Phenyl C61-butyric acid n-butyester), PCBIB (PhenylC61-ButyCyclicBhicC71-BictyPc) ester) and the like.
  • fullerene hydroxide, fullerene oxide, hydrogenated fullerene, and the like can also be used.
  • the rubber composition for tires according to the present invention can be obtained by kneading the above components using a conventional banbury, open roll, kneader, biaxial kneader or the like.
  • a vulcanizing agent In the tire rubber composition according to the present invention, a vulcanizing agent, a vulcanization aid, an anti-aging agent, a filler, a process oil, zinc white, stearic acid, and the like, which are usually used in the rubber industry, if necessary.
  • An agent may be kneaded.
  • vulcanizing agent known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, metal oxides such as magnesium oxide, and the like can be used.
  • the vulcanizing agent is preferably blended in an amount of about 0.5 to 3 parts by mass with respect to 100 parts by mass of the rubber component ( ⁇ ) + ( ⁇ ).
  • vulcanization aid known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates and xanthates can be used.
  • Anti-aging agents include amine / ketone series, imidazole series, amine series, phenol series, sulfur series and phosphorus series.
  • filler examples include inorganic fillers such as silica, calcium carbonate, basic magnesium carbonate, clay, Lissajous, and diatomaceous earth, and organic fillers such as carbon black, recycled rubber, and powder rubber.
  • inorganic fillers such as silica, calcium carbonate, basic magnesium carbonate, clay, Lissajous, and diatomaceous earth
  • organic fillers such as carbon black, recycled rubber, and powder rubber.
  • Process oil may be any of aromatic, naphthenic and paraffinic.
  • Measured / evaluated methods such as catalyst activity, physical properties of polybutadiene and physical properties of the composition are as follows.
  • Catalyst activity Polymer yield (g) per hour of polymerization time per 1 mmol of the central metal of the catalyst used in the polymerization reaction.
  • the catalyst is a gadolinium compound
  • it is the polymer yield (g) per hour of polymerization time per 1 g of gadolinium metal of the gadolinium compound used in the polymerization reaction.
  • Microstructure Performed by infrared absorption spectrum analysis. The microstructure was calculated from the absorption intensity ratio of cis 734 cm ⁇ 1 , trans 967 cm ⁇ 1 and vinyl 910 cm ⁇ 1 .
  • Number average molecular weight (Mn) and weight average molecular weight (Mw) Calibration performed from a molecular weight distribution curve obtained by GPC (manufactured by Shimadzu Corporation) at a temperature of 40 ° C. using polystyrene as a standard material and tetrahydrofuran as a solvent. The number average molecular weight and the weight average molecular weight were calculated using a line.
  • Mw / Mn which is a ratio of weight average molecular weight Mw and number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.
  • Mooney viscosity (ML 1 + 4 , 100 ° C.): According to JIS-K6300, pre-heated at 100 ° C. for 1 minute using a Mooney viscometer manufactured by Shimadzu Corporation, and then measured for 4 minutes to determine the Mooney viscosity (ML 1 + 4 , 100 ° C).
  • Polybutadiene is converted to polyethylene by hydrogenation while maintaining its branched structure, with long chain branching (branched chain having 6 or more carbon atoms) and short chain branching (ethyl group) derived from the vinyl-1,2 structure.
  • long chain branching branched chain having 6 or more carbon atoms
  • short chain branching ethyl group
  • 13 C-NMR normal single pulse
  • the long chain branching point present in a small amount in the polymer cannot be quantified due to the dynamic range caused by the main chain methylene peak.
  • the short chain branch point based on can be quantified sufficiently. That is, the quantitative relationship between the number of methylene carbons and the number of methine carbons can be obtained from the ratio of the peak area of the short chain branching point methine carbon peak to the peak area of the main chain methylene carbon peak.
  • the number of branch points (number of short chain branch points / 10,000 monomer units) can be determined.
  • Peak area S M of main chain methylene sum of peak areas of peak group [M1, M2, M3],
  • peak area S B of the short chain branching point methine is the peak area of the peak [B1]
  • the number of methylene carbons based on the cis-1,4 structure and the trans-1,4 structure is S M -S B (number proportional to), and the number of monomer units of the cis-1,4 structure and the trans-1,4 structure Is (S M ⁇ S B ) / 4 (a number proportional to).
  • the number of monomer units having the vinyl-1,2 structure, that is, the number of short chain branch points, is S B (number proportional to).
  • the number of short chain branch points per butadiene monomer unit (number of short chain branch points / 1 monomer unit) is S B / [(S M ⁇ S B ) / 4 + S B ] ⁇ 100 (mol%) (1) Can be calculated as
  • 13 C-NMR DEPT 90 ° measurement was performed at a measurement temperature of 130 ° C., an observation range of 10 to 42 ppm, and a cumulative number of 64,000 times in order to determine the ratio between the long chain branch points and the short chain branch points and the long chain branch points. .
  • the DEPT (Distortionless Enhancement by Polarization Transfer) method is a method for discriminating the series of carbons using the intensity change of the 13 C-NMR spectrum with respect to the pulse angle ( ⁇ ) to be irradiated.
  • the methyl and methylene carbon peaks disappear or greatly attenuate, and the methine carbon peak can be observed. That is, since the peak based on methylene carbon of the main chain of the hydrogenated polymer disappears or is greatly attenuated by DEPT 90 ° measurement, the dynamic range due to the main chain methylene peak having a large peak intensity, which is a problem in ordinary NMR measurement, is reduced. The problem is solved. As a result, a long chain branching point present in a minute amount in the polymer can be detected with high sensitivity.
  • the methine carbon at the short chain branch point and the methine carbon at the long chain branch point are observed as different peaks with quantifiable sensitivity (intensity, S / N ratio). That is, the ratio of the number of long chain branch points to the number of short chain branch points (number of long chain branch points / short chain) from the ratio of the peak area of the short chain branch point methine carbon peak to the peak area of the methine carbon peak of the long chain branch point.
  • the number of branch points can be obtained.
  • S L peak area of peak [L]
  • the number of long chain branch points per 10,000 butadiene monomer units can be calculated from (number of long chain branch points / number of short chain branch points). That is, the number of long chain branch points per 10,000 butadiene monomer units is (Number of long chain branch points / number of short chain branch points) ⁇ (number of short chain branch points / 1 monomer unit) ⁇ 10,000 Can be calculated as
  • Viscoelasticity measurement (measurement of Y (50%) / Y (10%) ): 7.5 g of polybutadiene was dissolved in 200 ml of toluene. Next, 7.5 g of liquid paraffin was added to this solution and stirred until uniform. The obtained solution was poured onto a stainless steel tray covered with a PET film, and then vacuum-dried at 60 ° C. for 8 hours using a vacuum dryer. The obtained liquid paraffin 50 mass% solution of polybutadiene was 15 g.
  • Polybutadiene 1.5g was dissolved in toluene 200ml. Next, 13.5 g of liquid paraffin was added to this solution and stirred until uniform. The obtained solution was poured onto a stainless steel tray covered with a PET film, and then vacuum-dried at 60 ° C. for 8 hours using a vacuum dryer. The liquid polyparaffin 10 mass% solution obtained was 15g.
  • the angular frequency dependence of the storage elastic modulus G ′ and loss elastic modulus G ′′ of the obtained polybutadiene in liquid paraffin 50% by mass and 10% by mass was measured.
  • the measurement was performed in a nitrogen stream using ARES manufactured by TA Instruments equipped with a parallel plate having a diameter of 25 mm or 7.9 mm.
  • the measurement frequency range is 100 to 0.01 rad / s, and the measurement temperatures are 0 ° C., 20 ° C., 40 ° C., 60 ° C., 80 ° C., and 100 ° C. J. et al. D.
  • Abrasion resistance (Lambourn wear resistance): Lambourn wear resistance was measured at a slip rate of 40% according to the measurement method defined in JIS-K6264, and indicated as an index with Comparative Example R1 shown in Table 3 as 100 ( The higher the index, the better.
  • Rebound resilience According to JIS-K6255, the rebound resilience was measured at room temperature using a Dunlop trypometer, and displayed as an index with Comparative Example R1 listed in Table 3 being 100 (the larger the index, the better).
  • Low fuel consumption (tan ⁇ (60 ° C.): Measured at a temperature range of ⁇ 120 ° C. to 100 ° C., a frequency of 16 Hz, and a dynamic strain of 0.3% using a viscoelasticity measuring device (manufactured by GABO, EPLEXOR 100N), 60 ° C. Tan ⁇ was used as an index of low fuel consumption. The index was displayed with the comparative example R1 described in Table 3 as 100. Low fuel consumption (tan ⁇ ) is better. In addition, the index in Table 3 is described so as to increase as fuel efficiency is improved.
  • Example 1 The inside of the autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 545 ml of cyclohexane solvent and 550 ml of butadiene was charged. Next, 3.4 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.88 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium (Gd (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 2 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 500 ml of cyclohexane solvent and 500 ml of butadiene was charged. Next, 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.80 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium (Gd (dpm) 3 ) was added, followed by hydrogenation.
  • TEAL triethylaluminum
  • Example 3 The inside of the autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 545 ml of cyclohexane solvent and 550 ml of butadiene was charged. Next, 3.4 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.88 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium (Gd (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 4 The inside of the 1.5 L autoclave was purged with nitrogen, and a solution consisting of 495 ml of cyclohexane solvent and 500 ml of butadiene was charged. Subsequently, 3.2 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.8 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium (Gd (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 5 The inside of the autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 545 ml of cyclohexane solvent and 550 ml of butadiene was charged. Subsequently, 2.85 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.88 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium (Gd (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 6 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 500 ml of cyclohexane solvent and 500 ml of butadiene was charged. Next, 3.4 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.4 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium (Tb (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 7 The inside of the autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 400 ml of cyclohexane solvent and 400 ml of butadiene was charged. Subsequently, 4.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.4 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium (Tb (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 8 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 295 ml of cyclohexane solvent and 300 ml of butadiene was charged. Subsequently, 1.8 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.24 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium (Tb (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 9 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 295 ml of cyclohexane solvent and 300 ml of butadiene was charged. Subsequently, 1.95 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.24 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium (Tb (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 10 The inside of the autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 545 ml of cyclohexane solvent and 550 ml of butadiene was charged. Next, 3.4 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.88 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium (Dy (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 11 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 295 ml of cyclohexane solvent and 300 ml of butadiene was charged. Subsequently, 1.95 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.48 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium (Dy (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 12 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Next, 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium (Dy (dpm) 3 ), triphenyl was added.
  • TEAL triethylaluminum
  • Example 13 The inside of the 1.5 L autoclave was purged with nitrogen, and a solution consisting of 495 ml of cyclohexane solvent and 500 ml of butadiene was charged. Subsequently, 2.7 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 1.0 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium (Ho (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 14 The inside of the 1.5 L autoclave was purged with nitrogen, and a solution consisting of 395 ml of cyclohexane solvent and 400 ml of butadiene was charged. Then, 2.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 1.6 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium (Tm (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 15 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Next, 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.5 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium (Er (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 16 The inside of the 1.5 L autoclave was purged with nitrogen, and a solution consisting of 495 ml of cyclohexane solvent and 500 ml of butadiene was charged. Next, 3.1 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 1.0 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium (Er (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • Example 17 The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Next, 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.5 ml of a cyclohexane solution (0.01 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium (Er (dpm) 3 ) was added, and then triphenyl was added.
  • TEAL triethylaluminum
  • the polybutadienes obtained in Examples 1 to 17 have a relatively large Tcp / ML 1 + 4 that is an index of molecular linearity (linearity) of 1.3 or more and 5.0 or less,
  • the cold flow rate (CF) is 5.5 mg / min or less, and the cold flow characteristics are excellent.
  • Example R1 Using the polybutadiene synthesized using Gd (dpm) 3 in Example 1, according to the formulation shown in Table 2, natural rubber, carbon black, zinc oxide, stearic acid, anti-aging agent and oil are added and kneaded with a plastmill. A primary compounding was carried out, and then a secondary compounding in which a vulcanization accelerator and sulfur were added by a roll was carried out to produce a compounded rubber. Further, this compounded rubber was molded according to the desired physical properties, and press vulcanized at 150 ° C. to produce a vulcanized product, and the physical properties were measured. Table 3 shows the measurement results of the physical properties of various blends.
  • Example R2 Using the polybutadiene synthesized using Tb (dpm) 3 in Example 6, according to the formulation shown in Table 2, natural rubber, carbon black, zinc oxide, stearic acid, anti-aging agent and oil are added and kneaded with a plastmill. A primary compounding was carried out, and then a secondary compounding in which a vulcanization accelerator and sulfur were added by a roll was carried out to produce a compounded rubber. Further, this compounded rubber was molded according to the desired physical properties, and press vulcanized at 150 ° C. to produce a vulcanized product, and the physical properties were measured. Table 3 shows the measurement results of the physical properties of various blends.
  • Example R3 Using the polybutadiene synthesized using Dy (dpm) 3 in Example 10, according to the formulation shown in Table 2, natural rubber, carbon black, zinc oxide, stearic acid, anti-aging agent and oil are added and kneaded with a plastmill. A primary compounding was carried out, and then a secondary compounding in which a vulcanization accelerator and sulfur were added by a roll was carried out to produce a compounded rubber. Further, this compounded rubber was molded according to the desired physical properties, and press vulcanized at 150 ° C. to produce a vulcanized product, and the physical properties were measured. Table 3 shows the measurement results of the physical properties of various blends.
  • Example R4 Using the polybutadiene synthesized using Ho (dpm) 3 in Example 13, according to the formulation shown in Table 2, natural rubber, carbon black, zinc oxide, stearic acid, anti-aging agent, and oil are added and kneaded with a plastmill. A primary compounding was carried out, and then a secondary compounding in which a vulcanization accelerator and sulfur were added by a roll was carried out to produce a compounded rubber. Further, this compounded rubber was molded according to the desired physical properties, and press vulcanized at 150 ° C. to produce a vulcanized product, and the physical properties were measured. Table 3 shows the measurement results of the physical properties of various blends.
  • Example R5 Using the polybutadiene synthesized using Er (dpm) 3 in Example 16, according to the formulation shown in Table 2, natural rubber, carbon black, zinc oxide, stearic acid, anti-aging agent and oil are added and kneaded with a plastmill. A primary compounding was carried out, and then a secondary compounding in which a vulcanization accelerator and sulfur were added by a roll was carried out to produce a compounded rubber. Further, this compounded rubber was molded according to the desired physical properties, and press vulcanized at 150 ° C. to produce a vulcanized product, and the physical properties were measured. Table 3 shows the measurement results of the physical properties of various blends.
  • Comparative Example R1 Primary blending by adding natural rubber, carbon black, zinc oxide, stearic acid, anti-aging agent and oil with plasto mill according to the blending formulation shown in Table 2, using JSR BR01 manufactured by JSR Corporation of Comparative Example 1 as polybutadiene. Then, the compounding rubber was produced by implementing the secondary compounding which adds a vulcanization accelerator and sulfur with a roll. Further, this compounded rubber was molded according to the desired physical properties, and press vulcanized at 150 ° C. to produce a vulcanized product, and the physical properties were measured. Table 3 shows the measurement results of the physical properties of various blends.
  • compositions of Examples R1 to R5 using the polybutadiene obtained in Examples 1, 6, 10, 13, and 16 are the compositions of Comparative Example R1 using JSR BR01 manufactured by JSR Corporation. It has superior rebound resilience, low-temperature storage elastic modulus at -30 ° C, and low fuel consumption (tan ⁇ (60 ° C)), and wear resistance, low heat build-up, and permanent set are equivalent or better.
  • a polybutadiene having excellent properties of a polybutadiene having a low degree of branching for example, excellent wear resistance, low heat generation, rebound resilience, and excellent cold flow properties. It can.
  • the polybutadiene of the present invention is excellent in wear resistance, low heat build-up, rebound resilience, and the like, and can be suitably used for rubber compositions, particularly tire rubber compositions.

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Abstract

Un mode de réalisation de la présente invention concerne un polybutadiène qui est caractérisé en ce qu'il présente : un rapport de la viscosité dans une solution de toluène à 5 % (Tcp) telle que mesurée à 25°C à la viscosité Mooney (ML1+4) à 100°C, à savoir (Tcp/ML1+4), de 1,3 à 5,0 (inclus) ; une distribution des poids moléculaires (Mw/Mn) de 2,0 ou plus mais inférieure à 4 ; et une vitesse de fluage à froid (CF) de 5,5 mg/min ou moins.
PCT/JP2015/069791 2014-09-12 2015-07-09 Polybutadiène et composition de caoutchouc WO2016039004A1 (fr)

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