WO2017061831A1 - 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 - Google Patents
변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 Download PDFInfo
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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
- 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
- C08F36/14—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 containing elements other than carbon and hydrogen
- C08F36/16—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 containing elements other than carbon and hydrogen containing halogen
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- 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
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- 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
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- 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
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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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
- 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
- C08F36/14—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 containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/12—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing tin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Definitions
- the present invention relates to a modified conjugated diene-based polymer having excellent affinity with a filler, a preparation method thereof, a rubber composition comprising the same, and a tire manufactured using the rubber composition.
- a method of reducing the hysteresis loss of the vulcanized rubber In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber.
- a repulsive elasticity of 50 ° C. to 80 ° C., tan ⁇ , Goodrich heating and the like are used as an evaluation index of the vulcanized rubber. That is, a rubber material having a high rebound elasticity at the above temperature or a small tan ⁇ or good rich heat generation is preferable.
- conjugated diene-based (co) polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. .
- SBR styrene-butadiene rubber
- BR butadiene rubber
- the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final SBR or BR rubber, and the movement of the chain ends by the binding or modification of the chain ends and the binding force with fillers such as silica or carbon black can be increased. Is widely used as a rubber material for tires.
- the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby controlling tire required properties such as running resistance and braking force, and properly adjusting the glass transition temperature. By adjusting the fuel consumption can be reduced.
- the solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers.
- US Pat. No. 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.
- carbon black and silica are used as reinforcing fillers for tire treads.
- silica is used as reinforcing fillers, low hysteresis loss and wet skid resistance are improved.
- the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler may be used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent.
- Patent Document 1 US 4,397,994 A
- the present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a modified conjugated diene polymer having excellent affinity with a filler.
- Another object of the present invention is to provide a method for producing the modified conjugated diene polymer.
- Still another object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer.
- Another object of the present invention is to provide a tire manufactured using the rubber composition.
- the present invention provides a modified conjugated diene-based polymer represented by the formula (1).
- R, R 4 and R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms
- R 2 and R 3 are each independently a hydrocarbon group of 1 to 20 carbon atoms or a hydrocarbon group of 1 to 20 carbon atoms containing oxygen or nitrogen,
- R 2 and R 3 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,
- P is a modified conjugated diene polymer chain
- X is a halogen group
- A is a tertiary amine
- a and b are each independently an integer of 1 to 4,
- the present invention is to prepare an active polymer in which alkali metals are bonded to both terminals by polymerizing conjugated diene monomer or aromatic vinyl monomer and conjugated diene monomer in the presence of a polyfunctional anionic polymerization initiator in a hydrocarbon solvent (Step 1 ); Reacting the polymer with a tin-based compound represented by Formula 2 (step 2); And it provides a method for producing the modified conjugated diene polymer represented by the formula (1) comprising the step (step 3) of reacting with the amino silane compound represented by the formula (3) after the reaction.
- R, R 4 and R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms
- R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group of 1 to 20 carbon atoms containing oxygen or nitrogen,
- R 2 and R 3 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,
- P is a modified conjugated diene polymer chain
- X is a halogen group
- A is a tertiary amine
- a, b and m are each independently an integer from 1 to 4,
- the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a tire produced using the rubber composition.
- the modified conjugated diene-based polymer according to the present invention has a tin compound-derived group bound to one end and a silane compound-derived group bound to the other end thereof, thereby having excellent affinity with not only silica filler but also carbon black filler. Can be.
- the processability of the rubber composition comprising the modified conjugated diene-based polymer may be excellent, and as a result, the processed product (eg, a tire) manufactured using the rubber composition may have excellent tensile strength, wear resistance, and viscoelastic properties. .
- the present invention provides a modified conjugated diene-based polymer having excellent affinity with not only silica-based fillers but also carbon black-based fillers, thereby improving workability.
- the modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that the compound represented by the formula (1).
- R, R 4 and R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms
- R 2 and R 3 are each independently a hydrocarbon group of 1 to 20 carbon atoms or a hydrocarbon group of 1 to 20 carbon atoms containing oxygen or nitrogen,
- R 2 and R 3 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,
- P is a modified conjugated diene polymer chain
- X is a halogen group
- A is a tertiary amine
- a and b are each independently an integer of 1 to 4,
- R, R 4 and R 5 are independently an alkyl group having 1 to 10 carbon atoms
- R 2 and R 3 are independently an alkyl group having 1 to 10
- R, R 4 and R 5 are independently an alkyl group having 1 to 6 carbon atoms, and R 2 and R 3 are independently of each other an alkyl group having 1 to 6 carbon atoms or containing carbon 1 It may be an alkyl group of 6 to.
- X may be selected from F, Cl, Br, and I.
- the modified conjugated diene-based polymer according to an embodiment of the present invention as shown in the structure of Formula 1, a group derived from a tin-based compound represented by Formula 2 described below is bonded to one end of the polymer, and the other end thereof is described later.
- An amino silane compound derived group represented by the formula (3) may be combined. That is, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a different functional group bonded to both ends.
- the modified conjugated diene-based polymer may contain 50 ppm to 550 ppm of tin (Sn), and may contain 80 ppm to 700 ppm of silica (Si).
- the tin may be one component constituting the tin-based compound-derived group
- the silica may be one component constituting the amino-silane-based compound-derived group.
- the modified conjugated diene-based polymer has a tin compound-derived group bound to one end and an amino silane compound-derived group bound to one end thereof, thereby making it compatible with not only silica filler but also carbon black filler.
- This can be excellent.
- the blending properties with the filler may be excellent, and thus, the processability of the rubber composition including the modified conjugated diene-based polymer may be excellent, and as a result, the tensile strength characteristics of the molded article, for example, a tire manufactured using the rubber composition, Viscoelastic properties can be improved.
- the modified conjugated diene polymer may be a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
- the modified conjugated diene polymer is a copolymer of a conjugated diene monomer and an aromatic vinyl monomer
- the copolymer may be a random copolymer
- random copolymer may indicate that the structural units constituting the copolymer are randomly arranged.
- the conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimenyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2- It may be one or more selected from the group consisting of phenyl-1,3-butadiene.
- the modified conjugated diene-based polymer when the modified conjugated diene-based polymer is a copolymer of a conjugated diene-based monomer and an aromatic vinyl monomer, the modified conjugated diene-based polymer may be 60% by weight or more, specifically 60% by weight to 90% by weight of a unit derived from a conjugated diene monomer.
- the content may include 60 wt% to 85 wt%.
- the aromatic vinyl monomer is not particularly limited, but for example, styrene, ⁇ -methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexyl styrene, 4- (p It may be one or more selected from the group consisting of -methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.
- the modified conjugated diene-based polymer when the modified conjugated diene-based polymer is a copolymer of a conjugated diene-based monomer and an aromatic vinyl monomer, the modified conjugated diene-based polymer may be 40% by weight or less, specifically 10 to 40% by weight of units derived from aromatic vinyl monomers. For example, the content may be 15 wt% to 40 wt%.
- derived unit may refer to a component, a structure, or the substance itself resulting from a substance.
- modified conjugated diene-based polymer may have a Mooney viscosity of 50 or more, specifically 50 to 150, more specifically 60 to 120.
- the modified conjugated diene polymer may have a number average molecular weight of 50,000 g / mol to 700,000 g / mol, specifically 100,000 g / mol to 500,000 g / mol, and more specifically 150,000 g / mol to 400,000 g / mol. .
- the modified conjugated diene-based polymer may have a weight average molecular weight of 250,000 g / mol to 1,600,000 g / mol.
- the modified conjugated diene-based polymer may have a vinyl content of 5% or more, specifically 10% or more, more specifically 10% to 50%, and within this range, the glass transition temperature of the polymer may be adjusted to an appropriate range. Therefore, when applied to the tire can not only meet the properties required for the tire, such as running resistance and braking force, but also has the effect of reducing fuel consumption.
- the vinyl content refers to the content of the 1,2-added conjugated diene monomer instead of 1,4-addition based on 100% by weight of the conjugated diene polymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.
- the modified conjugated diene-based polymer may have a PDI of 1.5 to 3.5, specifically 1.7 to 3.2, more specifically 2.0 to 3.0.
- the modified conjugated diene-based polymer has a characteristic of viscoelasticity, when measured at 10 Hz through DMA after silica blending, a Tan ⁇ value (Tan ⁇ at 0 ° C.) at 0 ° C. is 0.60 to 1.20, or 0.70 to 1.00, Within this range, there is an effect that the road surface resistance or the wetting resistance is significantly improved as compared with the conventional invention.
- Tan ⁇ value (Tan ⁇ at 60 ° C.) at 60 ° C. may be 0.08 to 0.14, or 0.09 to 0.13, and within this range, the rolling resistance or rotational resistance (RR) is greatly improved compared to the conventional invention. see.
- the present invention also provides a method for producing the modified conjugated diene polymer.
- the production method according to an embodiment of the present invention is an active polymer in which an alkali metal is bonded to both terminals by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in a polyfunctional anionic polymerization initiator in a hydrocarbon solvent.
- Preparing step 1; Reacting the polymer with a tin-based compound represented by Formula 2 (step 2); And reacting with the silane compound represented by the following Chemical Formula 3 after the reaction (step 3).
- R, R 4 and R 5 are each independently a hydrocarbon group having 1 to 20 carbon atoms
- R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms; C1-C20 hydrocarbon group containing oxygen; Or a hydrocarbon group of 1 to 20 carbon atoms containing nitrogen,
- R 2 and R 3 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,
- X is a halogen group
- A is a tertiary amine
- n is an integer of 1-4.
- Step 1 is a step for preparing an active polymer in which alkali metals are bonded to both ends, and is performed by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of a polyfunctional anionic polymerization initiator in a hydrocarbon solvent.
- a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of a polyfunctional anionic polymerization initiator in a hydrocarbon solvent.
- active polymer in which alkali metals are bonded at both ends may refer to a polymer in which anions and alkali metal cations are bonded at both ends of the polymer.
- the polymerization of step 1 may be one using a conjugated diene monomer alone or an aromatic vinyl monomer and a conjugated diene monomer together as described above. That is, the polymer prepared by the above production method according to an embodiment of the present invention may be a homopolymer derived from a conjugated diene monomer or a copolymer derived from an aromatic vinyl monomer and a conjugated diene monomer.
- conjugated diene monomer and the aromatic vinyl monomer may be as described above.
- amount of each monomer used is not particularly limited and may be used in an amount such that the conjugated diene monomer-derived unit and the aromatic vinyl monomer-derived unit in the modified conjugated diene-based polymer are prepared as described above.
- the hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclolock hexane, toluene, benzene and xylene.
- the multifunctional anionic polymerization initiator may be used in an amount of 0.10 parts by weight to 0.50 parts by weight based on 100 parts by weight of the total monomers.
- the polyfunctional anionic polymerization initiator may be prepared by reacting an aromatic compound with an organolithium compound in a hydrocarbon solvent. In this case, the aromatic compound and the organolithium compound may be reacted at a molar ratio of 1: 1 to 2.
- the aromatic compound used in the preparation of the polyfunctional anionic polymerization initiator is ⁇ -diisopropenyl benzene, m-diisopropenyl benzene, p-diisopropenyl benzene, ⁇ -divinylbenzene, m-divinylbenzene, p-divinylbenzene, 1,2,4-trivinylbenzene, 1,2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4 -Divinylbiphenyl, 3,5,4'-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene and 1,5,6-trivinyl-3,7-diethyl naphthalene It may be one or more selected from the group, but is not limited thereto.
- the organolithium compounds used in the preparation of the polyfunctional anionic polymerization initiator are ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium, lithium acetyl amide and lithium isopropylamide. It may be one or more selected from the group consisting of, but is not limited thereto.
- the hydrocarbon solvent used in the preparation of the multifunctional anionic polymerization initiator may be as described above.
- a Lewis base may be further used in the preparation of the multifunctional anionic polymerization initiator to promote or stabilize the production of the initiator.
- the Lewis base is not particularly limited, but may be used in an amount of 30 ppm to 70,000 ppm relative to the hydrocarbon solvent.
- the Lewis base can be used, for example, tertiary amines, tertiary diamines, chained or cyclic ethers and the like.
- the tertiary amine is trimethylamine, triethylamine, methyl diethylamine, 1,1-dimethoxy trimethylamine, 1,1-diethoxy trimethylamine, 1,1-diethoxy triethylamine, N, N-dimethyl Formamide diisopropyl acetal, N, N-dimethylformamide dicyclohexyl acetal, and the like.
- the tertiary diamine is N, N, N ', N'-tetramethyl diaminomethane, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethypropane diamine , N, N, N ', N'-tetramethyl diaminobutane, N, N, N', N'-tetramethyl diaminopentane, N, N, N ', N'-tetramethyl hexanediamine, dipiperi Dinopentane, dipiperidino ethane, and the like.
- the chain ether may be dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene dimethyl ether, or the like.
- the cyclic ether may be tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane, 2,2- Bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, etc. Can be.
- the polyfunctional anionic polymerization initiator may be prepared by reacting under a temperature of 50 ° C. or lower, specifically, a temperature condition of ⁇ 20 ° C. to 30 ° C.
- the polymerization of step 1 may be performed by further adding a polar additive, the polar additive may be added to 0.001 parts by weight to 5.0 parts by weight relative to 100 parts by weight of the total monomer. Specifically, the polar additive may be added at 0.005 parts by weight to 3.0 parts by weight based on 100 parts by weight of the total monomers.
- the polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, tertiary butoxyethoxyethane bis ( 3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.
- the reaction rate may be easily compensated for by forming a random copolymer. Can be induced.
- step 1 may be carried out through adiabatic polymerization, or isothermal polymerization.
- the adiabatic polymerization refers to a polymerization method including the step of polymerizing with a self-heating reaction without adding heat after the addition of the multifunctional anion polymerization initiator, and the isothermal polymerization is optionally after adding the polyfunctional anion polymerization initiator It refers to a polymerization method in which the temperature of the polymer is kept constant by applying heat or taking away heat.
- the polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically 0 ° C to 150 ° C, and more specifically 10 ° C to 120 ° C.
- Step 2 is a step of reacting the polymer with the tin-based compound represented by Chemical Formula 2 in order to bond a tin-based compound-derived group to one end of the active polymer having alkali metals bonded to both ends.
- the tin compound represented by the formula (2) is methyl trichloro tin, dimethyl dichloro tin, ethyl trichloro tin, diethyl dichloro tin, butyl trichloro tin, dibutyl dichloro tin, octyl trichloro tin, dioctyl From the group consisting of dichlorotin, methyl tribromotin, dimethyl dibromotin, octyl tribromotin, dioctyl dibromotin, tetrachlorotin, tetrabromotin, tetraiodide, cyclohexyl trichlorobutane and phenyltrichlorotin It may be one or more selected.
- the tin-based compound may be used in a ratio in which tin in the tin-based compound is 0.05 mol to 0.25 mol per 1 mol of lithium in the polyfunctional anionic polymerization initiator.
- Step 3 is a step of reacting the polymer with the amino silane compound represented by Formula 3 to bond the amino silane compound-derived group to the other end of the polymer having a tin compound-derived group bonded at one end thereof.
- amino silane compound represented by Chemical Formula 3 may be 3- (diethoxy (methyl) silyl) -N, N-diethylpropan-1-amine or 2- (N, N-dimethylaminopropyl) 2, It may be 5,5-trimethyl-1,3,2-dioxysilene.
- the silane-based compound may be used in a ratio of 0.1 mol to 1.0 mol of silica in the amino silane-based compound per mol of lithium in the polyfunctional anionic polymerization initiator.
- Each reaction in steps 2 and 3 is a modification reaction for bonding functional groups to both ends of the polymer, each reaction may be performed for 10 minutes to 5 hours in a temperature range of 10 °C to 120 °C. .
- the preparation method according to an embodiment of the present invention may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary after step 3 above.
- the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
- the rubber composition may include 20 wt% to 90 wt% of a modified conjugated diene-based polymer.
- the rubber composition may include 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, and the filler may be a silica-based filler, a carbon black-based filler, or a combination thereof.
- the rubber composition may further include other diene polymers as needed in addition to the modified conjugated diene polymer, and the diene polymer may be, for example, styrene-butadiene polymer, butadiene polymer, natural rubber, or a combination thereof. .
- the present invention provides a tire manufactured using the rubber composition.
- the tire may include a tire or a tire tread.
- the second reactor was also 80 ° C. and the reaction time was 60 minutes. Butadiene and styrene were consumed more than 99% through the second reactor, but the third and fourth reactors were also used to prepare the polymer under the same conditions as the other comparative polymers.
- Tin tetrachloride was added at a ratio of 0.25 times the number of moles of the anionic polymerization initiator used in the middle of the second reactor and the third reactor, and the tin coupling reaction occurred in the third reactor.
- the temperature of the 3rd and 4th reactors was 75 degreeC, respectively, and the time which a polymer stays in a reactor was 30 minutes, respectively.
- 2,6-di-t-butyl-p-cresol (BHT) was added to the reaction from the fourth reactor at 4.0 g / hr, the solvent was removed by steam stripping, dried over a roll mill, and modified conjugated diene.
- a polymer obtained was obtained, wherein the modified conjugated diene-based polymer has one end bonded to a tin compound-derived group, and the other end terminated with an amino silane compound-derived group.
- the presence or absence of the tin coupling reaction was confirmed by the difference in the Mooney viscosity of the second reactor polymer and the Mooney viscosity of the third reactor polymer. That is, when the Mooney viscosity rose, it was determined that a coupling reaction with tin occurred.
- modification reaction was carried out by using a modifier may be performed by mixing the polymer with a silica or a silica and carbon black mixed reinforcing agent, and then immersing the compound before crosslinking in a solvent to measure the amount of rubber that is not dissolved, that is, bound rubber (Bound-Rubber). It was confirmed by comparison with the amount of bound rubber of the unmodified conjugated diene-based polymer. In other words, as the amount of bound rubber increased, degeneration was considered to be more advanced.
- Bound rubber measurement was measured by weighing about 0.2 g of the compound that has been kneaded with the inorganic reinforcing agent in a shape of about 1 mm and weighing it in a 100 mesh wire mesh, immersing in toluene for 24 hours, and then drying. The weight was measured. The amount of polymer bound to the filler was calculated from the amount of components remaining undissolved to determine the proportion of polymer bound to the filler relative to the amount of polymer in the original blend. This value was used as the rate of denaturation.
- a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the amount of tin tetrachloride was reduced by 0.17 mole ratio with respect to the polymerization initiator.
- Example 1 TMEDA was added at 0.64 g / hr, and an anionic polymerization initiator was added at 0.690 g / hr, tin tetrachloride and 3- (diethoxy (methyl) silyl) -N, N-diethylpropane-1- Unmodified conjugated diene polymer was prepared in the same manner as in Example 1 except that no amine was added. However, 0.5 g / hr of methanol was added to the polymer from the fourth reactor to remove polymer activity, and 2,6-di-t-butyl-p-cresol (BHT) was added at 4.0 g / hr.
- BHT 2,6-di-t-butyl-p-cresol
- Example 1 In Example 1, except that TMEDA was added at 0.76 g / hr to an anionic polymerization initiator of 0.86 g / hr, and tin tetrachloride was not added. A modified conjugated diene-based polymer having a group derived from this amino silane compound was prepared.
- Comparative Example 2 in order to confirm the influence on the physical properties and processability by narrowing the molecular weight distribution of the polymer prepared than Comparative Example 2, the temperature of the first reactor was changed to 60 °C and the reaction time to 20 minutes, the second reactor The reaction time was extended to 80 minutes, and the amount of polymer was obtained in the same manner as in Comparative Example 2, except that TMEDA (tetramethyldetylenediamine) was added at 0.38 g / hr and an anionic polymerization initiator at 0.75 g / hr. A modified conjugated diene polymer having a terminal-derived aminosilane-based compound-derived group was prepared.
- TMEDA tetramethyldetylenediamine
- KOBELCO BB_L1600IM Intermeshing Banbury Mixer was used, and a rubber sheet was manufactured at 50 ° C and 6 inch rolls to make specimens for evaluation of physical properties.
- Table 1 such as rubber, silica, and stearic acid
- the inorganic filler was blended using two kinds of inorganic fillers: 50 parts by weight of silica and 20 parts by weight of carbon black, and 70 parts by weight of silica alone.
- Specimen crosslinking for measurement of physical properties was prepared using a press at 160 ° C. for 1.3 times for each formulation crosslinking rate (t′90).
- Rheology properties such as Tg, Wet Grip (0 ° C tan ⁇ ) and RR (60 ° C tan ⁇ ) of the crosslinked rubber were evaluated in Temperatue Sweep mode in the range of -40 ⁇ +70 using Eplexor 500 N equipment from Gabo, Germany. Evaluation conditions were measured at a temperature rising rate of 2 °C / min, Frequency 10 Hz, Static Strain 3.5%, Dynamic Strain 3.0%.
- Compounding agent Compound name / product name Parts by weight (phr) Remarks Rubber LG SSBR 100 Primary formulation Silica (silica + carbon black) Degussa 7000GR (7000GR + HAF) 70 (50 + 20) Oil TDAE 37.5 X50S (Degussa) 50% carbon black and 50% bis (3-triethoxysilylpropyltetrasulfan) 11.2 Stearic acid - 2.0 ZnO - 3.0 RD Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, Flexsys 2.0 6PPD N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, Flexsys 2.0 WAX - 1.0 DPG Diphenylguanidine, Flexsys 1.75 Secondary formulation sulfur - 1.5 CZ N-t-butyl-2-benzothiazyl sulfonamide, Flexsys 2.0
- Comparative Example 2 in which both ends were modified with only the tensile properties, wet grip properties, rolling resistance (RR) properties, and the like compared to Comparative Example 1, which is an unmodified polymer.
- the processability was slightly inferior to the base rubber at the difference in Mooney viscosity, ie, ⁇ Mooney viscosity, before and after mixing with the inorganic filler.
- Example 1 in which the molecular chain ends were modified with 3- (diethoxy (methyl) silyl) -N, N-diethylpropane-1-amine modifier after coupling with tin tetrachloride first, unmodified in Comparative Example 1
- the main physical properties are all improved compared to the polymer, and even when compared to Comparative Example 2 in which both ends are modified with an amino silane-based modifier, the RR properties are slightly decreased but the difference is not large, whereas the ⁇ Mooney viscosity difference is large After the Mooney viscosity is significantly lowered it can be seen that the workability is very excellent.
- Example 2 in which both tin coupling and amino silane-based modifications were performed, a good balance of main physical properties and processability was excellent.
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Abstract
Description
배합제 | 화합물명/제품명 | 중량부(phr) | 비고 |
고무 | LG SSBR | 100 | 1 차 배합 |
실리카(실리카+카본블랙) | Degussa 7000GR(7000GR+HAF) | 70(50+20) | |
Oil | TDAE | 37.5 | |
X50S(Degussa) | 50% 카본 블랙 및 50% 비스(3-트리에톡시실릴프로필테트라술판) | 11.2 | |
스테아르산 | - | 2.0 | |
ZnO | - | 3.0 | |
RD | 폴리머라이즈드 2,2,4-트리메칠-1,2-디하이드로퀴놀린, Flexsys | 2.0 | |
6PPD | N-1,3-디메틸부틸-N’-페닐-p-페닐렌디아민, Flexsys | 2.0 | |
WAX | - | 1.0 | |
DPG | 디페닐구아니딘, Flexsys | 1.75 | 2 차 배합 |
황 | - | 1.5 | |
CZ | N-t-부틸-2-벤조티아질 술폰아미드, Flexsys | 2.0 |
실시예 1 | 비교예 1 | 비교예 2 | 실시예 1 | 실시예 2 | 비교예 3 | ||
변성방법 | 주석계+아미노 실란계 | 미변성 | 아미노 실란계 | 주석계+아미노 실란계 | 주석계+아미노 실란계 | 아미노 실란계 | |
무기 충진제 종류 | 혼합 (실리카 50 중량부 + 카본블랙 20 중량부) | 실리카 70 중량부 | |||||
BaseRubber | No.2 반응기무니점도(ML1+4@100 ℃) | 38.7 | 96.9 | 59.0 | 38.7 | 38.7 | 62.3 |
최종 무니점도 | 98.6 | 98.1 | 64.0 | 98.6 | 70.4 | 68.8 | |
SM 함량, % | 27.0 | 26.0 | 26.0 | 27.0 | 26.2 | 26.2 | |
Vinyl함량, % | 38.3 | 38.5 | 38.2 | 38.3 | 38.3 | 37.0 | |
Mn * 105 | 2.80 | 2.60 | 1.69 | 2.80 | 2.34 | 2.23 | |
Mw * 105 | 8.51 | 7.57 | 4.89 | 8.51 | 6.99 | 5.88 | |
MWD | 3.03 | 2.92 | 2.90 | 3.03 | 2.99 | 2.64 | |
GreenCompound | Compound무니점도 | 72 | 115 | 87 | 87 | 63 | 102 |
Δ무니점도(Comp.-Base) | -26.6 | +16.9 | +23 | -11.6 | -7.4 | +33.2 | |
Bound RubberIndex, %100 | 131 | 100 | 123 | 129 | 128 | 137 | |
Tc’90, min | 18.45 | 17.81 | 17.17 | 17.10 | 17.32 | 16.30 | |
CuredRubber | 300% 모둘러스Index, % | 105 | 100 | 113 | 95 | 93 | 105 |
인장강도 Index% | 115 | 100 | 110 | 107 | 104 | 104 | |
신율 Index, % | 113 | 100 | 102 | 113 | 115 | 104 | |
Tg, ℃ | -11.7 | -12.3 | -11.8 | -11.8 | -11.2 | -13.8 | |
Wet GripIndex,%(0℃ tanδ기준) | 102 | 100 | 106 | 104 | 108 | 103 | |
RR Index, %(60℃ tanδ 기준) | 111 | 100 | 114 | 110 | 107 | 116 |
Claims (27)
- 하기 화학식 1로 표시되는 변성 공액디엔계 중합체:[화학식 1]상기 화학식 1에서,R, R4 및 R5는 서로 독립적으로 탄소수 1 내지 20의 탄화수소기이고,R2 및 R3는 서로 독립적으로 탄소수 1 내지 20의 탄화수소기 또는 산소 또는 질소를 함유한 탄소수 1 내지 20의 탄화수소기이고,R2 및 R3는 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며,P는 변성 공액디엔계 중합체 사슬이고,X는 할로겐기이고,A는 3급 아민이며,a 및 b는 서로 독립적으로 1 내지 4의 정수이며,a+b≤4이다.
- 청구항 1에 있어서,상기 화학식 1에서,R, R4 및 R5는 서로 독립적으로 탄소수 1 내지 10의 알킬기이고,R2 및 R3은 서로 독립적으로 1 내지 10의 알킬기; 산소를 함유한 탄소수 1 내지 10의 알킬기; 또는 질소를 함유한 탄소수 1내지 10의 알킬기인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 화학식 1에서,R, R4 및 R5는 서로 독립적으로 탄소수 1 내지 6의 알킬기이고,R2 및 R3은 서로 독립적으로 탄소수 1 내지 6의 알킬기 또는 산소를 함유한 탄소수 1 내지 6의 알킬기인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 화학식 1에서,X는 F, Cl, Br 및 I 중에서 선택된 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 80 ppm 내지 700 ppm의 실리카(Si)를 함유하는 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 50 ppm 내지 550 ppm의 주석(Sn)을 함유하는 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액디엔계 중합체는 공액디엔계 단량체 및 방향족 비닐계 단량체의 공중합체인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 공중합체는 방향족 비닐계 단량체 유래 단위를 40 중량% 이하로 포함하는 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 중량평균분자량이 250,000 g/mol 내지 1,600,000 g/mol인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 중량평균분자량(Mw) 및 수평균분자량(Mn)의 비(Mw/Mn)가 1.7 내지 3.5인 것인 변성 공액디엔계 중합체.
- 1) 탄화수소 용매 중에서, 다관능성 음이온 중합 개시제 존재 하 공액디엔계 단량체 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 양 말단에 알칼리 금속이 결합된 활성 중합체를 제조하는 단계;2) 상기 중합체를 하기 화학식 2로 표시되는 주석계 화합물과 반응시키는 단계; 및3) 상기 반응 후 하기 화학식 3으로 표시되는 아미노 실란계 화합물과 반응시키는 단계를 포함하는 하기 화학식 1로 표시되는 청구항 1의 변성 공액디엔계 중합체의 제조방법:[화학식 1][화학식 2][화학식 3]상기 화학식 1, 화학식 2 또는 화학식 3에서,R, R4 및 R5는 서로 독립적으로 탄소수 1 내지 20의 탄화수소기이고,R1, R2 및 R3은 서로 독립적으로 탄소수 1 내지 20의 탄화수소기; 또는 산소 또는 질소를 함유한 탄소수 1 내지 20의 탄화수소기이고,R2 및 R3는 서로 연결되어 탄소수 5 내지 20의 지방족 고리 또는 탄소수 6 내지 20의 방향족 고리를 형성할 수 있으며,P는 변성 공액디엔계 중합체 사슬이고,X는 할로겐기이고,A는 3급 아민이며,a, b 및 m은 서로 독립적으로 1 내지 4의 정수이며,는 1 내지 4의 정수이고, b는 1 내지 4의 정수이며,a+b≤4이다.
- 청구항 11에 있어서,상기 다관능성 음이온 중합 개시제는 탄화수소 용매 중에서 방향족 화합물과 유기리튬 화합물을 반응시켜 제조된 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 방향족 화합물과 유기리튬 화합물은 1: 1 내지 2 몰비로 반응시키는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 방향족 화합물은 o-디이소프로페닐 벤젠, m-디이소프로페닐 벤젠, p-디이소프로페닐 벤젠, o-디비닐 벤젠, m-디비닐 벤젠, p-디비닐 벤젠, 1,2,4-트리비닐 벤젠, 1,2-비닐-3,4-디메틸벤젠, 1,3-디비닐 나프탈렌, 1,3,5-트리비닐나프탈렌, 2,4-디비닐비페닐, 3,5,4'-트리베닐 비페닐, 1,2-디비닐-3,4-디메틸벤젠 및 1,5,6-트리비닐-3,7-디에틸 나프탈렌으로 이루어진 군으로부터 선택된 1종 이상인 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 유기리튬 화합물은 에틸리튬, 프로필리튬, n-부틸리튬, s-부틸리튬, t-부틸리튬, 헥실리튬, 페닐리튬, 리튬이데틸 아미드 및 리튬 이소프로필아미드로 이루어진 군으로부터 선택된 1종 이상인 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 다관능성 음이온 중합 개시제는 단량체 총 100 중량부를 기준으로 0.10 중량부 내지 0.5 중량부로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 화학식 2로 표시되는 주석계 화합물은 메틸 트리클로로주석, 디메틸 디클로로주석, 에틸 트리클로로주석, 디에틸 디클로로주석, 부틸 트리클로로주석, 디부틸 디클로로주석, 옥틸 트리클로로주석, 디옥틸 디클로로주석, 메틸 트리브로모주석, 디메틸 디브로모주석, 옥틸 트리브로모주석, 디옥틸 디브로모주석, 테트라클로로주석, 테트라브로모주석, 테트라요오드화주석, 사이클로헥실 트리클로로부석 및 페닐트리 클로로주석으로 이루어진 군으로부터 선택된 1종 이상인 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 11에 있어서,화학식 3으로 표시되는 아미노 실란계 화합물은 3-(디에톡시(메틸)실릴)-N,N-디에틸프로판-1-아민 또는 2-(N,N-디메틸아미노프로필)-2,5,5-트리메틸-1,3,2-디옥시실리넨인 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 화학식 2로 표시되는 주석계 화합물은 다관능성 음이온 중합 개시제 내 리튬 1 mol 당 주석계 화합물 내 주석이 0.05 mol 내지 0.25 mol이 되는 비율로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 화학식 3으로 표시되는 실란계 화합물은 다관능성 음이온 중합 개시제 내 리튬 1 mol 당 아미노 실란계 화합물 내 실리카가 0.1 mol 내지 1.0 mol이 되는 비율로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 단계 1)의 중합은 극성 첨가제를 더 첨가하여 수행하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 21에 있어서,상기 극성 첨가제는 단량체 총 100 중량부 대비 0.001 중량부 내지 5.0 중량부로 첨가하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 1의 변성 공액디엔계 중합체를 포함하는 고무 조성물.
- 청구항 23에 있어서,상기 고무 조성물은 변성 공액디엔계 중합체를 20 중량% 내지 90 중량%로 포함하는 것인 고무 조성물.
- 청구항 23에 있어서,상기 고무 조성물은 중합체 100 중량부에 대하여 0.1 중량부 내지 200 중량부의 충진제를 포함하는 것인 고무 조성물.
- 청구항 25에 있어서,상기 충진제는 실리카계 충진제, 카본블랙계 충진제 또는 이들 조합인 것인 고무 조성물.
- 청구항 23의 고무 조성물로부터 제조된 타이어.
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EP3246344B1 (en) | 2019-12-25 |
KR101889156B1 (ko) | 2018-09-20 |
KR20170042257A (ko) | 2017-04-18 |
EP3246344A4 (en) | 2018-01-10 |
JP2018510922A (ja) | 2018-04-19 |
JP6503075B2 (ja) | 2019-04-17 |
US10414841B2 (en) | 2019-09-17 |
CN107207655A (zh) | 2017-09-26 |
EP3246344A1 (en) | 2017-11-22 |
CN107207655B (zh) | 2019-11-08 |
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