WO2017111463A1 - 변성 공액디엔계 중합체, 이의 제조방법 및 변성제 - Google Patents
변성 공액디엔계 중합체, 이의 제조방법 및 변성제 Download PDFInfo
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- WO2017111463A1 WO2017111463A1 PCT/KR2016/015018 KR2016015018W WO2017111463A1 WO 2017111463 A1 WO2017111463 A1 WO 2017111463A1 KR 2016015018 W KR2016015018 W KR 2016015018W WO 2017111463 A1 WO2017111463 A1 WO 2017111463A1
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- Prior art keywords
- independently
- carbon atoms
- conjugated diene
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- alkyl group
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- 0 C*C[Si](C)*N(*N(CC1)CCN1[Si](C)(C)C)*[Si](C)*(C)(C)C Chemical compound C*C[Si](C)*N(*N(CC1)CCN1[Si](C)(C)C)*[Si](C)*(C)(C)C 0.000 description 5
- ZXIYMCGSSPHRBV-UHFFFAOYSA-N CCCC(C)C1CCCC1 Chemical compound CCCC(C)C1CCCC1 ZXIYMCGSSPHRBV-UHFFFAOYSA-N 0.000 description 2
Classifications
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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
-
- 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
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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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
- C08K3/34—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
- C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- 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 provides a rubber modifier, a conjugated diene-based polymer comprising a functional group derived from the modifier, a method for producing a modified conjugated diene-based polymer using the modifier, a rubber composition comprising the modified conjugated diene-based polymer, and a tire prepared from the rubber composition. It is about.
- 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.
- As an evaluation index of the vulcanized rubber a repulsive elasticity of 50 ° C to 80 ° C, Tan ⁇ , and the like are used. That is, a rubber material having a high resilience at the above temperature or a small Tan ⁇ 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 controlled by coupling or modification. Can be. Therefore, it is easy to change the structure of the final manufactured SBR or BR rubber, and the movement of the chain ends can be reduced by the binding or modification of the chain ends, and the bonding strength with fillers such as silica or carbon black can be increased. It 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, a monofunctional initiator, 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.
- the present invention has been made in order to solve the problems of the prior art, and an object of the present invention is to provide a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the formula (1) having a filler, especially a silica-based filler affinity functional group. .
- Another object of the present invention is to provide a method for producing a modified conjugated diene-based polymer using the modifier.
- Another object of the present invention is to provide a modifier represented by the formula (1) which can provide a filler, in particular a silica-based filler affinity functional group.
- Another object of the present invention to provide a rubber composition comprising the modified conjugated diene-based polymer.
- Another object of the present invention is to provide a tire made from the rubber composition.
- the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).
- R 1 is an alkyl, -SiR 12 R 13 R 14 or -R 15 A 1 to 10 carbon atoms,
- R 2 to R 4 are each independently an alkylene group having 1 to 10 carbon atoms
- R 5 to R 8 are each independently an alkyl group having 1 to 10 carbon atoms
- a and b are each independently an integer of 1 to 3
- R 12 to R 14 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,
- R 15 is an alkylene group having 1 to 10 carbon atoms
- A is a substituent represented by the following formula (2),
- R 16 and R 17 are each independently an alkylene group having 1 to 10 carbon atoms
- R 18 to R 21 are each independently an alkyl group having 1 to 10 carbon atoms
- c and d are each independently an integer of 1 to 3.
- the present invention is to prepare an active polymer in which the alkali metal is bonded to at least one end by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent (step 1 ); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (step 2) of reacting the active polymer with a modifier represented by the formula (1).
- R 1 is alkyl having 1 to 10 carbon atoms, —SiR 12 R 13 R 14 or —R 15 A,
- R 2 to R 4 are each independently an alkylene group having 1 to 10 carbon atoms
- R 5 to R 8 are each independently an alkyl group having 1 to 10 carbon atoms
- a and b are each independently an integer of 1 to 3
- R 12 to R 14 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,
- R 15 is an alkylene group having 1 to 10 carbon atoms
- A is a substituent represented by the following formula (2),
- R 16 and R 17 are each independently an alkylene group having 1 to 10 carbon atoms
- R 18 to R 21 are each independently an alkyl group having 1 to 10 carbon atoms
- c and d are each independently an integer of 1 to 3.
- R 1 is alkyl having 1 to 10 carbon atoms, —SiR 12 R 13 R 14 or —R 15 A,
- R 2 to R 4 are each independently an alkylene group having 1 to 10 carbon atoms
- R 5 to R 8 are each independently an alkyl group having 1 to 10 carbon atoms
- a and b are each independently an integer of 1 to 3
- R 12 to R 14 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,
- R 15 is an alkylene group having 1 to 10 carbon atoms
- A is a substituent represented by the following formula (2),
- R 16 and R 17 are each independently an alkylene group having 1 to 10 carbon atoms
- R 18 to R 21 are each independently an alkyl group having 1 to 10 carbon atoms
- c and d are each independently an integer of 1 to 3.
- the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a tire made from the rubber composition.
- the modified conjugated diene-based polymer according to the present invention may be excellent in affinity with the filler, in particular, silica-based filler, because the modified polymer-derived functional group represented by the formula (1), such as siloxane group and amine group in the polymer chain.
- the production method according to the present invention can easily prepare a modified conjugated diene-based polymer having excellent modification rate by using a modifier represented by the formula (1).
- the modifier represented by Formula 1 according to the present invention can be used as a modifier of the conjugated diene-based polymer, it is easy to introduce a filler affinity functional group by binding to the conjugated diene-based polymer chain.
- the rubber composition according to the present invention may be excellent in workability by including a modified conjugated diene-based polymer having excellent affinity with the filler, and as a result, the processed product (for example, a tire) manufactured using the rubber composition may be tensile. Strength and wet road resistance properties may be excellent.
- the present invention provides a modified conjugated diene-based polymer including a modifier-derived functional group represented by the following formula (1).
- R 1 is alkyl having 1 to 10 carbon atoms, —SiR 12 R 13 R 14 or —R 15 A,
- R 2 to R 4 are each independently an alkylene group having 1 to 10 carbon atoms
- R 5 to R 8 are independently an alkyl group having 1 to 10 carbon atoms with each other,
- a and b are each independently an integer of 1 to 3
- R 12 to R 14 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,
- R 15 is an alkylene group having 1 to 10 carbon atoms
- A is a substituent represented by the following formula (2),
- R 16 and R 17 are each independently an alkylene group having 1 to 10 carbon atoms
- R 18 to R 21 are each independently an alkyl group having 1 to 10 carbon atoms
- c and d are each independently an integer of 1 to 3.
- the modified conjugated diene-based polymer according to an embodiment of the present invention may include a modifier-derived functional group represented by the formula (1). That is, the modified conjugated diene-based polymer may be modified by a modifier represented by Formula (1).
- the modified conjugated diene-based polymer has a siloxane group and an amine group bonded to the polymer chain may be excellent in affinity with the filler, in particular silica filler. Accordingly, the physical properties of the rubber composition including the modified conjugated diene-based polymer may be excellent, and consequently, the tensile strength of a molded article, such as a tire, manufactured using the rubber composition may be excellent. Abrasion resistance and wet road resistance can be improved.
- the denaturing agent in Formula 1 R 1 is an alkyl group having 1 to 6 carbon atoms or -SiR 12 R 13 R 14 , wherein R 12 to R 14 are independently of each other an alkyl group having 1 to 6 carbon atoms or 1 carbon atoms Is an alkoxy group of 6 to 6, R 2, R 3 and R 4 are alkylene having 1 to 6 carbon atoms, R 5 to R 8 are independently alkyl of 1 to 6 carbon atoms, and a and b are each independently 1 It may be an integer of 3 to.
- R 1 is -R 15 A, R 2 To R 4 It is an alkylene group having 1 to 6 carbon atoms independently from each other, R 5 To R 8 It is Independently an alkyl group having 1 to 6 carbon atoms, a and b are each independently an integer of 1 to 3, wherein A is represented by Formula 2, wherein in Formula 2 R 15 to R 17 are independently of each other an alkylene group having 1 to 6 carbon atoms, R 18 to R 21 are independently an alkyl group having 1 to 6 carbon atoms from each other, c and d may be independently of each other an integer of 1 to 3.
- the modifier represented by Formula 1 may be one or more selected from the group consisting of modifiers represented by Formulas 3 to 5.
- R 2 to R 4 and R 15 to R 17 are each independently an alkylene group having 1 to 3 carbon atoms
- R 5 to R 8 and R 18 to R 21 are each independently an alkyl group having 1 to 3 carbon atoms, a to d may be an integer of 1 to 3 independently of each other.
- modified conjugated diene-based polymer including a modifier-derived functional group represented by the formula (1) may have a structure selected from polymers represented by the following formulas (6) to (8).
- R 2 to R 4 are each independently an alkylene group having 1 to 3 carbon atoms
- R 5 to R 8 are independently an alkyl group having 1 to 3 carbon atoms from each other,
- P is a polymer chain
- a, b, e, and f are each independently an integer from 0 to 3, e + f is an integer from 1 to 6,
- R 2 to R 4 and R 15 to R 17 are each independently an alkylene group having 1 to 3 carbon atoms
- R 5 to R 8 and R 18 to R 21 are each independently an alkyl group having 1 to 3 carbon atoms
- P is a polymer chain
- a to h are each independently an integer of 0 to 3
- e + f + g + h is an integer of 1 to 12.
- the modified conjugated diene-based polymer according to an embodiment of the present invention may be a homopolymer or a copolymer, it may be prepared by the manufacturing method described below.
- the modified conjugated diene polymer when it is a homopolymer, it may be a modified conjugated diene polymer, and when the modified conjugated diene polymer is a copolymer, the modified conjugated diene polymer may be a conjugated diene monomer-derived unit and an aromatic vinyl monomer. It may include a derived unit.
- the modified conjugated diene-based polymer when the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer.
- the "random copolymer” may indicate that the structural units constituting the copolymer are randomly arranged.
- the modified conjugated diene-based polymer may have a number average molecular weight of 1,000 g / mol to 2,000,000 g / mol, specifically 10,000 g / mol to 1,000,000 g / mol. More specifically, it may be from 100,000 g / mol to 1,000,000 g / mol.
- the modified conjugated diene-based polymer may have a weight average molecular weight of 10,000 g / mol to 3,000,000 g / mol, specifically may be 100,000 g / mol to 2,000,000 g / mol.
- the modified conjugated diene-based polymer may be a polydispersity index of 0.5 to 10, specifically 1 to 4.
- the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, and more specifically 10% by weight to 60% by weight.
- the glass transition temperature can be adjusted to an appropriate range, and when applied to a tire, not only the properties required for the tire such as running resistance and braking force are excellent, but also the fuel consumption is reduced.
- the vinyl content represents 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 or a conjugated diene monomer.
- the modified conjugated diene-based polymer has a characteristic of viscoelasticity, when measured at 10 Hz through DMA after silica blending, the Tan ⁇ value (Tan ⁇ at 0 ° C.) at 0 ° C. may be 0.4 to 1, and specifically, It may be from 0.5 to 1. If the above range is indicated, road surface resistance or wetting resistance may be significantly improved as compared with a conventional conjugated diene-based polymer.
- Tan ⁇ value (Tan ⁇ at 60 ° C.) at 60 ° C. may be 0.3 to 0.2 or 0.15 to 0.1. If the above range is indicated, the rolling resistance or rotational resistance (RR) can be significantly improved compared to the conventional conjugated diene-based polymer.
- the present invention provides a method for producing a modified conjugated diene-based polymer using a modifier represented by the formula (1).
- the production method according to an embodiment of the present invention is an active polymer in which an alkali metal is bonded to at least one terminal by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent.
- Preparing step 1
- And reacting the active polymer with a denaturant represented by Formula 1 below step 2.
- R 1 is alkyl having 1 to 10 carbon atoms, —SiR 12 R 13 R 14 or —R 15 A,
- R 2 to R 4 are each independently an alkylene group having 1 to 10 carbon atoms
- R 5 to R 8 are each independently an alkyl group having 1 to 10 carbon atoms
- a and b are each independently an integer of 1 to 3
- R 12 to R 14 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,
- R 15 is an alkylene group having 1 to 10 carbon atoms
- A is a substituent represented by the following formula (2),
- R 16 and R 17 are independently C 1 -C 10 alkylene group of one another
- R 18 to R 21 are each independently an alkyl group having 1 to 10 carbon atoms
- c and d are each independently an integer of 1 to 3.
- Step 1 is a step for preparing an active polymer having an alkali metal bonded to at least one end thereof, and is performed by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent.
- a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent.
- the polymerization in step 1 may be one using a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer together. 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 a conjugated diene monomer and an aromatic vinyl monomer. In addition, when the conjugated diene-based polymer is a copolymer, as described above, the copolymer may be a random copolymer.
- the conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.
- the conjugated diene-based monomer may be 50 wt% or more, specifically, in the finally prepared modified conjugated diene-based polymer. It may be used in an amount comprised from 50% to 95% by weight, more specifically from 60% to 95% by weight.
- the aromatic vinyl monomer is not particularly limited, but for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p It may be one or more selected from the group consisting of -methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.
- the aromatic vinyl monomer may have 50% by weight or less of the unit derived from the aromatic vinyl monomer in the finally prepared modified conjugated diene polymer. 5 wt% to 50 wt%, more specifically 5 wt% to 40 wt% may be used.
- the "derived unit” may refer to a component, a structure, or the substance itself resulting from a substance.
- 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, cyclohexane, toluene, benzene and xylene.
- the organoalkali metal compound is used in an amount of 0.01 mmol to 10 mmol, specifically 0.05 mmol to 5 mmol, more specifically 0.1 mmol to 2 mmol, and even more specifically 0.1 mmol to 1 mmol, based on 100 g of the total monomer. It may be.
- the organoalkali metal compound is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, Phenyllithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naph At least one selected from the group consisting of sodium sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropy
- the polymerization of step 1 may be performed by further adding a polar additive as needed, the polar additive may be added to 0.001 parts by weight to 50 parts by weight based on 100 parts by weight of the total monomer. Specifically, the content may be added in an amount of 0.001 part by weight to 10 parts by weight, more specifically 0.005 parts by weight to 1 part by weight, and more specifically 0.005 parts by weight to 0.1 parts by weight, based on 100 parts by weight of the total monomer.
- the polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis It may be one or more selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.
- the reaction rate can be easily compensated for by forming a random copolymer. Can be induced.
- the polymerization of step 1 may be, for example, anionic polymerization, and specifically, may be living anion polymerization of obtaining an active terminal by a growth reaction by anions.
- step 1 may be carried out through adiabatic polymerization, or isothermal polymerization, may be a batch (batch) or a continuous polymerization comprising one or more reactors.
- adiabatic polymerization refers to a polymerization method including a step of polymerizing with self-heating reaction without adding heat after the addition of the organoalkali metal compound, and the isothermal polymerization is an arbitrary heat after adding the organoalkali metal compound. It represents a polymerization method for maintaining a constant temperature of the polymer by adding 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 active polymer with a modifier represented by Formula 1 to prepare a modified conjugated diene-based polymer.
- the modifier represented by Chemical Formula 1 may be the same as described above.
- the modifying agent represented by Chemical Formula 1 may be used in an amount of 0.1 mol to 10 mol, specifically 0.3 mol to 2 mol, relative to 1 mol of the organic alkali metal compound. If the denaturant represented by Formula 1 is used in the above ratio, the denaturation reaction may be effectively performed.
- the reaction of step 2 according to an embodiment of the present invention is a modification reaction for introducing a functional group into the polymer, each reaction may be performed for 1 minute to 5 hours in the 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 2 above.
- the present invention provides a modifier that can provide an affinity functional group with reinforcing fillers, especially silica-based fillers.
- the denaturing agent according to an embodiment of the present invention is characterized by represented by the following formula (1).
- R 1 is alkyl having 1 to 10 carbon atoms, —SiR 12 R 13 R 14 or —R 15 A,
- R 2 to R 4 are each independently an alkylene group having 1 to 10 carbon atoms
- R 5 to R 8 are independently an alkyl group having 1 to 10 carbon atoms with each other,
- a and b are each independently an integer of 1 to 3
- R 12 to R 14 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,
- R 15 is an alkylene group having 1 to 10 carbon atoms
- A is a substituent represented by the following formula (2),
- R 16 and R 17 are each independently an alkylene group having 1 to 10 carbon atoms
- R 18 to R 21 are each independently an alkyl group having 1 to 10 carbon atoms
- c and d are each independently an integer of 1 to 3.
- the modifier represented by Formula 1 may be a modifier for a conjugated diene polymer.
- the conjugated diene polymer may be a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
- the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
- the rubber composition according to an embodiment of the present invention may be a modified conjugated diene-based polymer containing 10 wt% or more, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt%. have. If the content of the modified conjugated diene-based polymer is less than 10% by weight, the effect of improving the wear resistance and crack resistance of a molded article, for example, a tire manufactured using the rubber composition may be insignificant.
- the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition.
- the rubber composition may include 20 parts by weight to 100 parts by weight of the modified conjugated diene-based polymer and 0 parts by weight to 80 parts by weight of other rubber components based on 100 parts by weight of the rubber composition.
- the rubber composition according to another embodiment of the present invention is 10 parts by weight to 100 parts by weight of the modified conjugated diene-based polymer, 0 parts by weight to 90 parts by weight of other rubber components, 0 parts by weight to 100 parts by weight of carbon black, 5 parts by weight to 200 parts by weight of silica and 2 parts by weight to 20 parts by weight of the silane coupling agent, wherein the parts by weight are based on 100 parts by weight of the total amount of the modified conjugated diene-based polymer and other rubber components.
- the rubber composition according to another embodiment of the present invention comprises 10% to 99% by weight of the modified conjugated diene-based polymer and 1% to 90% by weight of the other rubber component, the modified conjugated diene-based polymer And about 1 part by weight to 100 parts by weight of carbon black, about 5 parts by weight to about 200 parts by weight of silica, and about 2 parts by weight to about 20 parts by weight of the silane coupling agent, based on 100 parts by weight of the total of the other high component.
- the rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-d
- the rubber composition according to another embodiment of the present invention may include 0.1 to 200 parts by weight of inorganic filler based on 100 parts by weight of the modified conjugated diene-based polymer.
- the rubber composition according to another embodiment of the present invention may include 10 parts by weight to 150 parts by weight, specifically 50 parts by weight to 100 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.
- the filler may be a silica-based filler, a carbon black-based filler, or a combination thereof.
- the silica-based filler when used as the filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by combining the silica particles of the filler with the modified conjugated diene-based polymer terminal.
- the rubber composition according to an embodiment of the present invention may be used with a silane coupling agent to improve the reinforcement and low heat generation when using a silica-based filler as a filler.
- silane coupling agent examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N
- the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.
- a modified conjugated diene-based polymer having a functional group having high affinity with a silica-based filler as an active moiety is used as the rubber component.
- the compounding amount can be reduced than usual.
- the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the silica-based filler. When used in the above range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.
- the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.
- the vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.
- the rubber composition according to an embodiment of the present invention in addition to the components described above, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
- the said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used.
- the vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.
- the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance.
- naphthenic or paraffinic process oils may be used when considering low temperature properties.
- the process oil may be included in an amount of 5 parts by weight to 100 parts by weight, specifically 20 parts by weight to 80 parts by weight, based on 100 parts by weight of the rubber component, and when included in the content, tensile strength of the vulcanized rubber, low heat generation It is possible to prevent deterioration of the properties (low fuel efficiency).
- the anti-aging agent specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone.
- the anti-aging agent may be used in an amount of 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the rubber component.
- the rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.
- a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc.
- the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.
- the present invention provides a tire manufactured using the rubber composition.
- the tire may include a tire or a tire tread.
- SM Styrene derived units
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each copolymer were measured by gel permeation chromatograph (GPC) analysis under 40 ° C.
- the column (column) was used in combination with two bags of PLgel Olexis of Polymer Laboratories Co., Ltd. and one PLgel mixed-C column, all of the newly replaced column was a mixed bed column.
- PS polystyrene
- the polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by the above method.
- the Mooney viscosity of each copolymer was measured by MV-2000 (Alpha Technologies Co., Ltd.) for 15 minutes or more of each sample weight 15g or more for 1 minute and then at 100 °C for 4 minutes.
- the styrene-butadiene copolymer of Comparative Example 1 was prepared through the same conditions as the modified styrene-butadiene copolymer of Examples 1 to 3, except that the modification was not performed.
- Table 1 shows that the modified styrene-butadiene copolymer of Example 3 has an increase in Mooney viscosity compared to the styrene-butadiene copolymer of Comparative Example 1 is the modified styrene-butadiene copolymer of Examples 1 to 3 It indicates that denaturation has been made.
- Each rubber composition was prepared through a first stage kneading process and a second stage kneading process. At this time, the amount of the substance except the modified conjugated diene copolymer is shown based on 100 parts by weight of the modified conjugated diene copolymer.
- the first stage kneading 137.5 parts by weight of each modified conjugated diene copolymer, 70 parts by weight of silica, bis (3-triethoxysilylpropyl) tetrasulfate as a silane coupling agent using a half-variety mixer equipped with a temperature controller.
- Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester to obtain tensile strength and tensile stress at 300% elongation.
- the viscoelastic properties were measured by using a dynamic mechanical analyzer (TA, Inc.) at a frequency of 10 Hz in the torsion mode and the deformation at each measurement temperature (-60 ° C to 60 ° C) to measure Tan ⁇ . It is represented by exponential index as a reference value. At this time, the exponentiation was calculated through the following equation (1) and (2).
- Equations 1 and 2 the reference value is the measured value of Comparative Example 2, and the measured value is the measured value of the remaining Examples and Comparative Examples.
- the styrene of Comparative Examples 1 and 2 wherein the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 to 3 prepared using the modifier according to the embodiment of the present invention is not modified. It was confirmed that the Tan ⁇ value at 0 ° C. increased (Index value improved) and the Tan ⁇ value decreased at 60 ° C. (Index value improved) compared to a rubber composition including butadiene copolymer. This is a result showing that the modified styrene-butadiene copolymer prepared by using the modifier according to an embodiment of the present invention has excellent resistance and rolling resistance characteristics on wet road surface, and high fuel efficiency.
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Abstract
Description
구분 | 스티렌 유래단위(wt%) | 비닐 (wt%) | GPC | 무니점도(MV) | ||
Mw(g/mol, X104) | Mn(g/mol, X104) | PDI | ||||
실시예 1 | 27 | 43 | 41 | 31 | 1.3 | 70 |
실시예 2 | 27 | 43 | 42 | 32 | 1.3 | 72 |
실시예 3 | 27 | 43 | 55 | 38 | 1.4 | 76 |
비교예 1 | 27 | 43 | 50 | 31 | 1.2 | 64 |
비교예 2 | 27 | 43 | 69 | 39 | 1.8 | 61 |
구분 | 실시예 1 | 실시예 2 | 실시예 3 | 비교예 1 | 비교예 2 | |
인장특성 | 인장강도(kgf/cm2) | 183 | 184 | 188 | 168 | 167 |
300% 인장응력(kgf/cm2) | 118 | 119 | 122 | 104 | 98 | |
점탄성 | Tan δat 0℃(Index) | 102 | 102 | 105 | 98 | 100 |
Tan δ60℃(Index) | 131 | 133 | 137 | 105 | 100 |
Claims (18)
- 하기 화학식 1로 표시되는 변성제 유래 작용기를 포함하는 변성 공액디엔계 중합체:[화학식 1]상기 화학식 1에서,R1은 탄소수 1 내지 10의 알킬기, -SiR12R13R14 또는 -R15A이고,R2 내지 R4는 서로 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R5 내지 R8은 서로 독립적으로 탄소수 1 내지 10의 알킬기이고,a 및 b는 서로 독립적으로 1 내지 3의 정수이며,상기에서 R12 내지 R14는 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 1 내지 10의 알콕시기이고,상기 R15는 탄소수 1 내지 10의 알킬렌기이고,상기 A는 하기 화학식 2로 표시되는 치환기이며,[화학식 2]상기 화학식 2에서,R16 및 R17은 서로 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R18 내지 R21은 서로 독립적으로 탄소수 1 내지 10의 알킬기이며,c 및 d는 서로 독립적으로 1 내지 3의 정수이다.
- 청구항 1에 있어서,상기 화학식 1에서,R1은 탄소수 1 내지 6의 알킬기 또는 -SiR12R13R14이고,여기에서 상기 R12 내지 R14는 서로 독립적으로 탄소수 1 내지 6의 알킬기이고,R2 내지 R4는 서로 독립적으로 탄소수 1 내지 6의 알킬렌기이고,R5 내지 R8은 서로 독립적으로 탄소수 1 내지 6의 알킬기이고,a 및 b는 서로 독립적으로 1 내지 3의 정수인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 화학식 1 또는 화학식 2에서,R1은 -R15A이고,R2 내지 R4 및 R15 내지 R17은 서로 독립적으로 탄소수 1 내지 6의 알킬렌기이고,R5 내지 R8 및 R18 내지 R21은 서로 독립적으로 탄소수 1 내지 6의 알킬기이고,a 내지 d는 서로 독립적으로 1 내지 3의 정수인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 공액디엔계 단량체 단독 중합체 또는 공액디엔계 단량체와 방향족 비닐계 단량체의 공중합체인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 하기 화학식 6 내지 화학식 8로 표시되는 중합체 중에서 선택된 것인 변성 공액디엔계 중합체:[화학식 6][화학식 7]상기 화학식 6 및 화학식 7에 있어서,R2 내지 R4는 서로 독립적으로 탄소수 1 내지 3의 알킬렌기이고,R5 내지 R8은 서로 독립적으로 탄소수 1 내지 3의 알킬기이고,P는 중합체 사슬이고,a, b, e 및 f는 서로 독립적으로 0 내지 3의 정수이되, e+f는 1 내지 6의 정수이고,[화학식 8]상기 화학식 8에 있어서,R2 내지 R4 및 R15 내지 R17은 서로 독립적으로 탄소수 1 내지 3의 알킬렌기이고,R5 내지 R8 및 R18 내지 R21은 서로 독립적으로 탄소수 1 내지 3의 알킬기이고,P는 중합체 사슬이고,a 내지 h는 서로 독립적으로 0 내지 3의 정수이되, e+f+g+h는 1 내지 12의 정수이다.
- 청구항 1에 있어서,상기 중합체는 수평균분자량이 1,000 g/mol 내지 2,000,000 g/mol인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 다분산지수가 0.5 내지 10인 것인 변성 공액디엔계 중합체.
- 청구항 1에 있어서,상기 중합체는 비닐 함량이 5 중량% 이상인 것인 변성 공액디엔계 중합체.
- 1) 탄화수소 용매 중에서, 유기 알칼리금속 화합물 존재 하에서 공액디엔계 단량체 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 적어도 일 말단에 알칼리 금속이 결합된 활성 중합체를 제조하는 단계; 및2) 상기 활성 중합체를 하기 화학식 1로 표시되는 변성제와 반응시키는 단계를 포함하는 청구항 1에 기재된 변성 공액디엔계 중합체의 제조방법:[화학식 1]상기 화학식 1에서,R1은 탄소수 1 내지 10의 알킬기, -SiR12R13R14 또는 -R15A이고,R2 내지 R4는 서로 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R5 내지 R8은 서로 독립적으로 탄소수 1 내지 10의 알킬기이고,a 및 b는 서로 독립적으로 1 내지 3의 정수이며,상기에서 R12 내지 R14는 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 1 내지 10의 알콕시기이고,상기 R15는 탄소수 1 내지 10의 알킬렌기이고,상기 A는 하기 화학식 2로 표시되는 치환기이며,[화학식 2]상기 화학식 2에서,R16 및 R17은 서로 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R18 내지 R21은 서로 독립적으로 탄소수 1 내지 10의 알킬기이며,c 및 d는 서로 독립적으로 1 내지 3의 정수이다.
- 청구항 10에 있어서,상기 유기 알칼리금속 화합물은 단량체 총 100 g을 기준으로 0.01 mmol 내지 10 mmol로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 10에 있어서,상기 유기 알칼리금속 화합물은 메틸리튬, 에틸리튬, 프로필리튬, n-부틸리튬, s-부틸리튬, t-부틸리튬, 헥실리튬, n-데실리튬, t-옥틸리튬, 페닐리튬, 1-나프틸리튬, n-에이코실리튬, 4-부틸페닐리튬, 4-톨릴리튬, 사이클로헥실리튬, 3,5-디-n-헵틸사이클로헥실리튬, 4-사이클로펜틸리튬, 나프틸나트륨, 나프틸칼륨, 리튬 알콕사이드, 나트륨 알콕사이드, 칼륨 알콕사이드, 리튬 술포네이트, 나트륨 술포네이트, 칼륨 술포네이트, 리튬 아미드, 나트륨 아미드, 칼륨아미드, 리튬 이소프로필아미드로 이루어진 군으로부터 선택된 1종 이상인 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 10에 있어서,상기 단계 1)의 중합은 극성 첨가제를 더 첨가하여 수행하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 13에 있어서,상기 극성 첨가제는 단량체 총 100 중량부 대비 0.001 중량부 내지 50 중량부로 첨가하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 10에 있어서,상기 화학식 1로 표시되는 변성제는 유기 알칼리금속 화합물 1 몰 대비 0.1 몰 내지 10 몰로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 하기 화학식 1로 표시되는 변성제:[화학식 1]상기 화학식 1에서,R1은 탄소수 1 내지 10의 알킬기, -SiR12R13R14 또는 -R15A이고,R2 내지 R4는 서로 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R5 내지 R8은 서로 독립적으로 탄소수 1 내지 10의 알킬기이고,a 및 b는 서로 독립적으로 0 내지 3의 정수이며,상기에서 R12 내지 R14는 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 1 내지 10의 알콕시기이고,상기 R15는 탄소수 1 내지 10의 알킬렌기이고,상기 A는 하기 화학식 2로 표시되는 치환기이며,[화학식 2]상기 화학식 2에서,R16 및 R17은 서로 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R18 내지 R21은 서로 독립적으로 탄소수 1 내지 10의 알킬기이며,c 및 d는 서로 독립적으로 0 내지 3의 정수이다.
- 청구항 17에 있어서,상기 변성제는 공액디엔계 단량체 단독 중합체 또는 공액디엔계 단량체와 방향족 비닐계 단량체의 공중합체 변성용 변성제인 것인 변성제.
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CN111212858A (zh) * | 2018-05-08 | 2020-05-29 | 株式会社Lg化学 | 改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物 |
WO2021066543A1 (ko) * | 2019-09-30 | 2021-04-08 | 주식회사 엘지화학 | 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 |
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CN111212858A (zh) * | 2018-05-08 | 2020-05-29 | 株式会社Lg化学 | 改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物 |
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CN111212858B (zh) * | 2018-05-08 | 2022-12-02 | 株式会社Lg化学 | 改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物 |
RU2812593C1 (ru) * | 2019-09-27 | 2024-01-30 | ЭлДжи КЕМ, ЛТД. | Модификатор, модифицированный полимер на основе сопряженного диена, содержащий этот модификатор, и способ получения полимера |
WO2021066543A1 (ko) * | 2019-09-30 | 2021-04-08 | 주식회사 엘지화학 | 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 |
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