WO2015056994A1 - 말단 기능성 공액 디엔계 중합체 및 이의 제조방법 - Google Patents
말단 기능성 공액 디엔계 중합체 및 이의 제조방법 Download PDFInfo
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- WO2015056994A1 WO2015056994A1 PCT/KR2014/009735 KR2014009735W WO2015056994A1 WO 2015056994 A1 WO2015056994 A1 WO 2015056994A1 KR 2014009735 W KR2014009735 W KR 2014009735W WO 2015056994 A1 WO2015056994 A1 WO 2015056994A1
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- conjugated diene
- formula
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- 0 CN(C)*N1CN(C)CC1 Chemical compound CN(C)*N1CN(C)CC1 0.000 description 6
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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
- C08C19/25—Incorporating silicon atoms into the molecule
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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
- B60C1/0016—Compositions of the tread
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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
- C08C19/30—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
- 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
- C08F236/10—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 with vinyl-aromatic monomers
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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
- C08L15/00—Compositions of rubber derivatives
Definitions
- the present invention relates to a terminal functional conjugated diene polymer and a preparation method thereof, and more particularly, to a terminal functional conjugated diene system having excellent compatibility with inorganic fillers, exothermicity, tensile strength, wear resistance, low fuel consumption, and wet road resistance. It relates to a polymer and a method for producing the same.
- the tire tread was used in combination with an inorganic filler in order to reinforce the above properties in the conjugated diene rubber, but there was a problem in that the hysteresis loss was large or the dispersibility was inferior.
- JP WO2005-097845 A1 a study on a method for producing a modified conjugated diene-based polymer has been conducted, but the effect is insufficient.
- the problem to be solved by the present invention is to provide a modified conjugated diene-based polymer excellent in compatibility with the inorganic filler and processability.
- Another object of the present invention is to provide a method for producing the modified conjugated diene polymer.
- Another object of the present invention is to provide a rubber composition excellent in exothermicity, tensile strength, wear resistance, low fuel consumption and wet road resistance, including the modified conjugated diene-based polymer.
- Another object of the present invention is to provide a rubber composition and a tire comprising the same.
- a modified conjugated diene-based polymer represented by the following formula (1) is provided:
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or each independently an alkyl group having 1 to 10 carbon atoms
- P is a conjugated diene polymer chain
- B is the following formula (13)
- a and c are each independently 0, 1, or 2
- b and d Are each independently 1, 2, or 3
- a + b and c + d are each independently 1, 2, or 3
- A is, or
- R 9 , R 10 , R 11 , and R 12 are Each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D is NR 3 R 4 or an oxygen-containing group
- R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 3 and R 4 are bonded to each other to form a heterocycle including N; Can be achieved.
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or each independently an alkyl group having 1 to 10 carbon atoms
- a and c are each independently 0, 1, or 2
- A is or
- R 9 , R 10 , R 11 , and R 12 are Each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D is NR 3 R 4 or an oxygen-containing group
- R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 3 and R 4 are bonded to each other to form a heterocycle including N; Can be achieved.
- a modified conjugated diene-based polymer rubber composition comprising 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of an inorganic filler.
- a tire using the modified conjugated diene-based polymer rubber composition is provided.
- a modified conjugated diene-based polymer having excellent compatibility with the inorganic filler and improved processability by using a rubber composition comprising such modified conjugated diene-based polymer, exothermic Tires with excellent rolling resistance, low tensile resistance, abrasion resistance, low fuel consumption and wet road resistance can be provided.
- Figure 1 shows the size of the tensile test piece of the rubber composition prepared according to the present invention.
- Modified conjugated diene-based polymer according to an aspect of the present invention is represented by the formula (1):
- R1, R2, and R5 are each independently an alkylene group having 1 to 10 carbon atoms
- R3, R4, R6, and R7 are each independently an alkyl group having 1 to 10 carbon atoms
- R8 is hydrogen or each independently An alkyl group having 1 to 10 carbon atoms
- P is a conjugated diene-based polymer chain
- B is a general formula (13)
- a and c are each independently 0, 1, or 2
- b and d are each independently 1, 2, Or 3
- a + b and c + d are each independently 1, 2, or 3
- A is or
- R9, R10, R11, and R12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. to be.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D contains NR 3 or oxygen Is one group
- R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
- the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 100,000 to 1,000,000 g / mol.
- Mn number average molecular weight
- the modification reaction may have the best or good physical properties.
- the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 0.5 to 10, preferably 0.5 to 5, more preferably 1 to 4.
- Mw / Mn molecular weight distribution
- mixing with inorganic particles is excellent, so that physical properties may be improved, and workability may be greatly improved.
- the modified conjugated diene-based polymer may have a vinyl content of 10% by weight or more, preferably 15% by weight or more, more preferably 20 to 70% by weight.
- the vinyl content refers to the content of the monomer having a vinyl group, or the content of 1,2-added conjugated diene monomer rather than 1,4-addition based on 100% by weight of the conjugated diene monomer.
- the glass transition temperature of the polymer is increased to not only satisfy the properties required for the tire such as running resistance and braking force when applied to the tire, but also consume fuel. Has the effect of reducing
- the conjugated diene-based polymer chain represented by P in Formula 1 may be derived from a homopolymer of conjugated diene-based monomer or a copolymer of conjugated diene-based monomer and vinyl aromatic monomer.
- the conjugated diene polymer chain is a homopolymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in a batch or continuous process in a hydrocarbon solvent in the presence of an organoalkali metal compound.
- a copolymer may be formed by reaction with a silyl group substituted with one or more alkoxy groups.
- the conjugated diene polymer chain is conjugated diene monomer. It may be a polymer chain comprising 0.0001 to 50 parts by weight, 10 to 40 parts by weight or 20 to 40 parts by weight of the aromatic vinyl monomer based on a total of 100 parts by weight of the conjugated diene monomer and the vinyl aromatic monomer.
- the polymer chain consisting of the conjugated diene monomer and the vinyl aromatic monomer may be, for example, a random polymer chain.
- the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
- the vinyl aromatic monomers are, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1 It may be at least one selected from the group consisting of -vinyl-5-hexyl naphthalene, and as another example, may be styrene or ⁇ -methylstyrene.
- the modified conjugated diene-based polymer may have a Mooney viscosity of 40 or more, preferably 40 to 100, more preferably 45 to 90.
- Mooney viscosity has such a range, a modified conjugated diene polymer having excellent workability, compatibility, exothermicity, tensile strength, abrasion resistance, low fuel efficiency and wet road surface resistance can be prepared.
- Modified conjugated diene-based polymer according to an embodiment of the present invention may be represented by the following formula (2) or (3):
- R15, R16, R18, R19, R22, R23, R25, and R26 are each independently an alkyl group having 1 to 5 carbon atoms
- R13, R14, R17, R20, R21, and R24 are each Independently an alkylene group having 1 to 5 carbon atoms
- P is a conjugated diene polymer chain
- B is the following formula (13)
- a and c are each independently 0, 1, or 2
- b and d are each independently 1 , 2, or 3
- a + b and c + d are each independently 1, 2, or 3.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D contains NR 3 or oxygen Is one group
- R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
- modified conjugated diene-based polymer may be represented by the following formula (4) or (5):
- P is a conjugated diene-based polymer chain
- B is the formula (13)
- a and c are each independently 0, 1, or 2
- b and d are each independently 1, 2, Or 3
- a + b and c + d are each independently 1, 2, or 3.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D contains NR 3 or oxygen Is one group
- R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
- the modified conjugated diene-based polymer may be represented by the following formula (6) or formula (7):
- Formula 1 is a modified conjugated diene-based polymer, characterized in that represented by the following formula (6) or formula (7):
- P is a conjugated diene polymer chain
- B is the following Chemical Formula 13.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D contains NR 3 or oxygen Is one group
- R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
- R1, R2, and R5 are each independently an alkylene group having 1 to 10 carbon atoms
- R3, R4, R6, and R7 are each independently an alkyl group having 1 to 10 carbon atoms
- R8 is hydrogen or each independently An alkyl group having 1 to 10 carbon atoms
- a and c are each independently 0, 1, or 2
- A is or
- R9, R10, R11, and R12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. to be.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D contains NR 3 or oxygen Is one group
- R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
- conjugated diene monomer and the vinyl aromatic monomer are as described above.
- the solvent is not particularly limited as long as it is a solvent that can be applied to homopolymerization or copolymerization of conjugated diene monomers, and examples thereof include hydrocarbons or n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and It may be at least one selected from the group consisting of xylene.
- the organometallic compound may be at least one selected from the group consisting of an organoalkali metal compound, an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.
- the organometallic compound may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyl At least one selected from the group consisting of lithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium have.
- the organometallic compound may be n-butyllithium, sec-butyllithium or a mixture thereof.
- the organometallic compound is a group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide It may be one or more selected from, and may also be used in combination with other organometallic compounds.
- the organometallic compound may be used as 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol or 0.1 to 1 mmol based on 100 g of the total monomer.
- an optimal conjugated diene-based polymer for preparing a modified conjugated diene-based polymer can be made.
- the molar ratio of the organometallic compound and the compound represented by Formula 8 is, for example, 1: 0.1 to 1:10, preferably 1: 0.3 to 1: 2. When the molar ratio satisfies this range, it is possible to give the modified reaction of optimal performance to the conjugated diene-based polymer.
- the active polymer having the metal end means a polymer in which a polymer anion and a metal cation are bonded.
- the modified conjugated diene-based polymer manufacturing method may be carried out by further adding a polar additive during the polymerization in the step (a).
- the reason why the polar additive is further added is that the polar additive controls the reaction rate of the conjugated diene monomer and the vinyl aromatic monomer.
- the polar additive may be a base or an ether, an amine or a mixture thereof, and specifically, tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether With diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine It may be selected from the group consisting of, preferably ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.
- the polar additive may be used in 0.001 to 50 g, 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 100 g of the monomer to be added.
- the polar additive may be used in 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 1 mmol of the organometallic compound introduced.
- the polymerization of (a) may be, for example, anionic polymerization, and specifically, the polymerization of (a) may be a living anion polymerization that obtains active ends by growth reaction by anions.
- polymerization of (a) may be, for example, elevated temperature polymerization or constant temperature polymerization.
- the elevated temperature polymerization refers to a polymerization method including a step of raising the reaction temperature by adding heat optionally after adding the organometallic compound, and the constant temperature polymerization means a polymerization method in which no heat is optionally added after adding the organometallic compound. .
- the polymerization temperature of (a) may be, for example, -20 to 200 °C, 0 to 150 °C or 10 to 120 °C.
- the end-capping reaction of step (b) may be a step of introducing the formula (13).
- step (b) may be a step of reacting for 1 minute to 5 hours at 0 to 90 °C, for example.
- the step (c) may be a step of injecting one or more, or two to three kinds of compounds represented by the formula (8).
- step (c) may be a step of reacting for 1 minute to 5 hours at 0 to 90 °C, for example.
- the modified conjugated diene-based polymer production method may be a batch polymerization (batch), or a continuous polymerization method including one or more reactors, for example.
- the compound of Formula 8 may be represented by, for example, the following Formula 9 or Formula 10:
- a and c are each independently 0, 1, or 2.
- a modified conjugated diene polymer prepared according to the above-described method for producing a modified conjugated diene polymer.
- the modified conjugated diene-based polymer may be represented by the following Chemical Formula 1.
- R1, R2, and R5 are each independently an alkylene group having 1 to 10 carbon atoms
- R3, R4, R6, and R7 are each independently an alkyl group having 1 to 10 carbon atoms
- R8 is hydrogen or each independently An alkyl group having 1 to 10 carbon atoms
- P is a conjugated diene-based polymer chain
- B is a general formula (13)
- a and c are each independently 0, 1, or 2
- b and d are each independently 1, 2, Or 3
- a + b and c + d are each independently 1, 2, or 3
- A is or
- R9, R10, R11, and R12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. to be.
- R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 2 is a bond or an alkylene group having 1 to 5 carbon atoms
- D contains NR 3 or oxygen Is one group
- R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
- the modified conjugated diene polymer has a characteristic of viscoelasticity, and when measured at 10 Hz through DMA after silica blending, the Tan ⁇ value at 0 ° C. (Tan ⁇ at 0 ° C.) is, for example, 0.4 to 1 or 0.5 to 1 In this range, there is an effect that the road surface resistance or wetting resistance is significantly improved compared to the conventional invention.
- Tan ⁇ value (Tan ⁇ at 60 ° C.) at 60 ° C. may be, for example, 0.3 to 0.2, or 0.15 to 0.1, and within this range, the rolling resistance or rotational resistance (RR) is greatly improved as compared with the conventional invention. Effect.
- a modified conjugated diene-based polymer rubber composition comprising 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of the inorganic filler.
- the inorganic filler may be, for example, 10 to 150 parts by weight, or 50 to 100 parts by weight.
- the inorganic filler may be at least one selected from the group consisting of silica-based fillers, carbon black, and mixtures thereof.
- silica-based fillers When the inorganic filler is a silica-based filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles with the ends of the modified conjugated diene-based polymer of the present invention.
- the modified conjugated diene-based polymer rubber composition may further include another conjugated diene-based polymer.
- the other conjugated diene-based polymer may be styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber, or a mixture thereof.
- SBR styrene-butadiene rubber
- BR butadiene rubber
- natural rubber or a mixture thereof.
- SBR may be, for example, solution styrene-butadiene rubber (SSBR).
- the modified conjugated diene-based polymer rubber composition may be one containing 20 to 100 parts by weight of the modified conjugated diene-based polymer and 0 to 80 parts by weight of the other conjugated diene-based polymer. have.
- the modified conjugated diene-based polymer rubber composition of the present invention may include 20 to 99 parts by weight of the modified conjugated diene-based polymer and 1 to 80 parts by weight of the other conjugated diene-based polymer.
- the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 To 200 parts by weight and 2 to 20 parts by weight of the silane coupling agent.
- the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 To 200 parts by weight and 2 to 20 parts by weight of the silane coupling agent, the sum of the weight of the modified conjugated diene-based polymer and other conjugated diene-based polymer may be 100 parts by weight.
- the modified conjugated diene-based polymer rubber composition of the present invention is 100 parts by weight of the polymer mixture comprising 10 to 99% by weight of the modified conjugated diene-based polymer and 1 to 90% by weight of the conjugated diene-based polymer It may include 1 to 100 parts by weight of black, 5 to 200 parts by weight of silica and 2 to 20 parts by weight of the silane coupling agent.
- the modified conjugated diene-based polymer rubber composition may further include 1 to 100 parts by weight of oil.
- the oil may be, for example, a mineral oil or a softener.
- the oil may be used in an amount of 10 to 100 parts by weight or 20 to 80 parts by weight based on 100 parts by weight of the conjugated diene-based copolymer, and exhibits good physical properties within this range, and further softens the rubber composition so that workability may be improved. Excellent effect.
- the tire or tire tread is manufactured using a rubber composition comprising a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved processability, thereby providing excellent rolling strength, wear resistance, and wet road resistance. It has the advantage of low resistance.
- N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added and reacted for 15 minutes. Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added.
- BHT butylated hydroxytoluene
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added and reacted for 15 minutes. Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added.
- BHT butylated hydroxytoluene
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added and reacted for 15 minutes. Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added.
- BHT butylated hydroxytoluene
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- Table 2 shows the analysis results of the most unmodified conjugated diene-based polymer (5025-2HM grade, manufactured by Lanses Irish GmbH).
- N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added and reacted for 15 minutes. Thereafter, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added.
- BHT butylated hydroxytoluene
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 2 below.
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 2 below.
- Mooney Viscosity ALPHA Technologies Inc. MV-2000 was used to preheat for 1 minute using two or more specimens weighing 15g and measured for 4 minutes at 100 °C.
- Mw Weight average molecular weight
- Mn number average molecular weight
- PDI molecular weight distribution
- Example 2 sample A B C Initiator (mmole) 4 2.5 4 Modified monomer end end I Denaturant a a a Mooney viscosity (MV) 65 95 64 Styrene (%) 27.0 27.4 27.0 vinyl(%) 40.9 39.8 44.0 Oil - - - GPC (x10 4 ) Mn 34.0 43.4 36.0 Mw 45.3 56.0 52.0 PDI 1.3 1.3 1.4
- the rubber composition of the conjugated diene-based polymer is kneaded through a total of first stage kneading and second stage kneading.
- a semi-barrier mixer equipped with a temperature controller is used to prepare raw rubber (conjugated diene polymer), filler, organosilane coupling agent, oil, galvanizing agent, stearic acid antioxidant, antioxidant, wax and accelerator. Kneaded. At this time, the temperature of the kneader was controlled, and the primary blend was obtained at the discharge temperature of 145-155 degreeC.
- Tan ⁇ was measured by changing the strain at a frequency of 10 Hz and each measurement temperature (-60 to 60 ° C.) in the torsion mode.
- the Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain.
- the smaller the Faye effect the better the dispersibility of the filler such as silica.
- the higher the low temperature 0 [deg.] C. Tan ⁇ the better the wet road surface resistance.
- the lower the high temperature 60 [deg.] C. Tan ⁇ the lower the hysteresis loss and the lower the rolling resistance of the tire, that is, the lower the fuel efficiency.
- Table 4 shows the physical properties of the vulcanized rubber.
- the tan ⁇ value at 0 ° C. is higher than that of Comparative Preparation Example 1 (unmodified). (Wet road resistance) was improved, Tan ⁇ value at 60 ° C. was low, and RR (cloud resistance) was also improved, and it was confirmed that fuel efficiency was good.
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Abstract
Description
구분 | 실시예 1 | 실시예 2 | 실시예 3 | |
시료 | A | B | C | |
개시제 (mmole) | 4 | 2.5 | 4 | |
변성 monomer | 가 | 가 | 나 | |
변성제 | a | a | a | |
무니점도 (MV) | 65 | 95 | 64 | |
스타이렌 (%) | 27.0 | 27.4 | 27.0 | |
비닐(%) | 40.9 | 39.8 | 44.0 | |
Oil | - | - | - | |
GPC(x104) | Mn | 34.0 | 43.4 | 36.0 |
Mw | 45.3 | 56.0 | 52.0 | |
PDI | 1.3 | 1.3 | 1.4 |
구분 | 비교예 1 | 비교예 2 | 비교예 3 | |
시료 | D | E | F | |
개시제 (mmole) | - | 4 | 4 | |
변성 monomer | - | - | 가 | |
변성제 | - | a | - | |
무니점도 (MV) | 61 | 88 | 63 | |
스타이렌 (%) | 26.0 | 27.0 | 27.0 | |
비닐(%) | 50.0 | 41.0 | 40.0 | |
Oil | TDAE (37.5 phr) | - | - | |
GPC(x104) | Mn | 39.0 | 38.0 | 36.0 |
Mw | 69.0 | 55.0 | 47.0 | |
PDI | 1.8 | 1.4 | 1.3 |
구분 | 물질 | 함량(단위: phr) |
제1 단 혼련 | 고무 | 137.5 |
실리카 | 70.0 | |
커플링제 | 11.2 | |
오일 | - | |
아연화제 | 3.0 | |
스테아르산 | 2.0 | |
산화방지제 | 2.0 | |
노화방지제 | 2.0 | |
왁스 | 1.0 | |
제2 단 혼련 | 고무촉진제 | 1.75 |
황 | 1.5 | |
가황촉진제 | 2.0 | |
총 중량 | 234.0 |
구분 | 시험예1 | 시험예2 | 시험예3 | 비교시험예1 | 비교시험예2 | 비교시험예3 |
시료 | 제조예1 | 제조예2 | 제조예3 | 비교제조예1 | 비교제조예2 | 비교제조예3 |
60℃ ΔG’ | 100 | 100 | 122 | 78 | 100 | 88 |
Tan δ at 0℃ | 100 | 110 | 95 | 70 | 100 | 105 |
Tan δ at 60℃ | 0.26 | 0.28 | 0.26 | 0.56 | 0.29 | 0.28 |
Claims (23)
- 하기 화학식 1로 표시되는 변성 공액 디엔계 중합체:<화학식 1>상기 화학식 1에서, R1, R2, 및 R5 는 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고, R3, R4, R6 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, R8은 수소 또는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공액 디엔계 중합체 사슬이고, B는 하기 화학식 13이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이고, A는 , 또는 이고, R9, R10, R11, 및 R12는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이다.<화학식 13>(상기 식에서, n 은 1 또는 2이며, R1은 수소, 또는 탄소의 개수가 1~5개인 알킬기, R2는 결합, 또는 탄소의 개수가 1~5개인 알킬렌기이며, D는 NR3R4 또는 산소를 함유한 기이고, 상기 R3 및 R4는 각각 독립적으로 수소, 또는 탄소의 개수가 1~5개인 알킬기이고, 상기 R3 및 R4는 서로 결합되어 N을 포함하는 복소환을 이룰 수 있다.)
- 청구항 1에 있어서,상기 화학식 1은 하기 화학식 2 또는 화학식 3으로 표시되는 것을 특징으로 하는 변성 공액 디엔계 중합체:<화학식 2><화학식 3>상기 화학식 2 및 화학식 3에서, R15, R16, R18, R19, R22, R23, R25, 및 R26 은 각각 독립적으로 탄소수 1 내지 5의 알킬기이고, R13, R14, R17, R20, R21, 및 R24 는 각각 독립적으로 탄소수 1 내지 5의 알킬렌기이고, P는 공액 디엔계 중합체 사슬이고, B는 하기 화학식 13이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이다.<화학식 13>(상기 식에서, n 은 1 또는 2이며, R1은 수소, 또는 탄소의 개수가 1~5개인 알킬기, R2는 결합, 또는 탄소의 개수가 1~5개인 알킬렌기이며, D는 NR3R4 또는 산소를 함유한 기이고, 상기 R3 및 R4는 각각 독립적으로 수소, 또는 탄소의 개수가 1~5개인 알킬기이고, 상기 R3 및 R4는 서로 결합되어 N을 포함하는 복소환을 이룰 수 있다.)
- 청구항 1에 있어서,상기 화학식 1은 하기 화학식 4 또는 화학식 5로 표시되는 것을 특징으로 하는 변성 공액 디엔계 중합체:<화학식 4><화학식 5>상기 화학식 4 및 화학식 5에서, P는 공액 디엔계 중합체 사슬이고, B는 하기 화학식 13이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이다.<화학식 13>(상기 식에서, n 은 1 또는 2이며, R1은 수소, 또는 탄소의 개수가 1~5개인 알킬기, R2는 결합, 또는 탄소의 개수가 1~5개인 알킬렌기이며, D는 NR3R4 또는 산소를 함유한 기이고, 상기 R3 및 R4는 각각 독립적으로 수소, 또는 탄소의 개수가 1~5개인 알킬기이고, 상기 R3 및 R4는 서로 결합되어 N을 포함하는 복소환을 이룰 수 있다.)
- 청구항 1에 있어서,상기 화학식 13은 4,4'-비닐리덴 비스(n,n-디메틸아닐린) (4,4'-vinylidenebis(n,n-dimethylaniline)), 3-(2-피롤리디노 에틸)스티렌 (3-(2-Pyrrolidino Ethyl)styrene)), 4-(2-피롤리디노 에틸)스티렌 (4-(2-Pyrrolidino Ethyl)styrene)) 및 (3-(2-피롤리디노-1-메틸에틸)-알파-메틸스티렌으로 이루어지는 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는 1,000 내지 2,000,000 g/mol의 수평균분자량(Mn)을 가지는 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는 0.5 내지 10의 분자량 분포(Mw/Mn)를 가지는 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는, 비닐 함량이 10 중량% 이상인 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 공액 디엔계 중합체 사슬은 공액 디엔계 단량체의 단독 중합체 또는 공액 디엔계 단량체와 비닐 방향족 단량체의 공중합체로부터 유래된 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는, 공액 디엔계 단량체와 방향족 비닐계 단량체를 합한 총 100 중량부를 기준으로 방향족 비닐계 단량체가 0.0001 내지 50 중량부로 포함된 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는 40 이상의 무니점도를 갖는 것을 특징으로 하는 변성 공액 디엔계 중합체.
- (a) 공액 디엔계 단량체, 또는 공액 디엔계 단량체와 비닐 방향족 단량체를 용매 하에서 유기금속 화합물을 이용하여 중합시켜 금속 말단을 갖는 활성 중합체를 형성하는 단계;(b) 알칼리 금속 말단을 갖는 활성 중합체를 하기 화학식 13으로 표시되는 화합물로 엔드-캡핑(end-capping) 시키는 단계; 및(c) 상기 활성 중합체에 하기 화학식 8로 표시되는 화합물을 투입하여 변성시키는 단계를 포함하는 변성 공액 디엔계 중합체의 제조방법:<화학식 8>상기 화학식 8에서, R1, R2, 및 R5 는 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고, R3, R4, R6 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, R8은 수소 또는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, A는 , 또는 이고, R9, R10, R11, 및 R12는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이다.
- 청구항 12에 있어서,상기 화학식 13은 4,4'-비닐리덴 비스(n,n-디메틸아닐린) (4,4'-vinylidenebis(n,n-dimethylaniline)), 3-(2-피롤리디노 에틸)스티렌 (3-(2-Pyrrolidino Ethyl)styrene)), 4-(2-피롤리디노 에틸)스티렌 (4-(2-Pyrrolidino Ethyl)styrene)) 및 (3-(2-피롤리디노-1-메틸에틸)-알파-메틸스티렌으로 이루어지는 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 유기금속 화합물은, 상기 단량체 총 100 g을 기준으로 0.01 내지 10 mmol로 사용되는 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 유기금속 화합물과 상기 화학식 8로 표시되는 화합물의 몰비는 1:0.1 내지 1:10인 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 (a) 단계에서 극성첨가제가 더 투입되는 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 18에 있어서,상기 극성첨가제는 상기 유기금속 화합물 총 1 mmol을 기준으로 0.001 내지 10 g으로 투입되는 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 12 내지 청구항 19 중 어느 한 항의 변성 공액 디엔계 중합체의 제조방법에 따라 제조되어 하기 화학식 1로 표시되는 변성 공액 디엔계 중합체:<화학식 1>상기 화학식 1에서, R1, R2, 및 R5 는 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고, R3, R4, R6 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, R8은 수소 또는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공액 디엔계 중합체 사슬이고, B는 하기 화학식 13이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이고, A는 , 또는 이고, R9, R10, R11, 및 R12는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이다.<화학식 13>(상기 식에서, n 은 1 또는 2이며, R1은 수소, 또는 탄소의 개수가 1~5개인 알킬기, R2는 결합, 또는 탄소의 개수가 1~5개인 알킬렌기이며, D는 NR3R4 또는 산소를 함유한 기이고, 상기 R3 및 R4는 각각 독립적으로 수소, 또는 탄소의 개수가 1~5개인 알킬기이고, 상기 R3 및 R4는 서로 결합되어 N을 포함하는 복소환을 이룰 수 있다.)
- 청구항 1 내지 청구항 11 중 어느 한 항의 변성 공액 디엔계 중합체 100 중량부, 및 무기 충진제 0.1 내지 200 중량부를 포함하는 변성 공액 디엔계 중합체 고무 조성물.
- 청구항 21에 있어서,상기 무기 충진제는 실리카계 충진제, 카본 블랙 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 변성 공액 디엔계 중합체 고무 조성물.
- 청구항 21의 변성 공액 디엔계 중합체 고무 조성물을 포함하는 타이어 또는 타이어 트레드.
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US10538599B2 (en) | 2015-12-18 | 2020-01-21 | Lg Chem, Ltd. | Modified polymer, method of preparing the same, and rubber composition including the modified polymer |
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CN108350118A (zh) * | 2016-04-25 | 2018-07-31 | 株式会社Lg化学 | 改性共轭二烯类聚合物及其制备方法 |
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