WO2015057021A1 - 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 - Google Patents
변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 Download PDFInfo
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- WO2015057021A1 WO2015057021A1 PCT/KR2014/009801 KR2014009801W WO2015057021A1 WO 2015057021 A1 WO2015057021 A1 WO 2015057021A1 KR 2014009801 W KR2014009801 W KR 2014009801W WO 2015057021 A1 WO2015057021 A1 WO 2015057021A1
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- conjugated diene
- formula
- based polymer
- independently
- modified conjugated
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- 0 CCS(*)*N(C)*N1C=NCC1 Chemical compound CCS(*)*N(C)*N1C=NCC1 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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- 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
- C08C19/25—Incorporating silicon 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
- 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 method for producing a modified conjugated diene-based polymer, and more particularly, a method for preparing a modified conjugated diene-based polymer having excellent exothermicity, tensile strength, abrasion resistance, and wet road resistance, prepared by using the same.
- Modified conjugated diene-based polymer, and a rubber composition comprising the same.
- the inventors of the present invention have proposed the present invention to develop a rubber having a high heat resistance and a tensile strength, abrasion resistance, and wet road resistance as a tire tread material.
- An object of the present invention is to provide a modified conjugated diene-based polymer having excellent exothermicity, tensile strength, abrasion resistance, and wet road resistance, and a method for producing the conjugated diene polymer.
- an object of the present invention is to provide a modified conjugated diene-based polymer rubber composition comprising the modified conjugated diene-based polymer.
- Another problem to be solved by the present invention is to provide a modifier used in the preparation of the modified conjugated diene-based polymer.
- Another object of the present invention is to provide a rubber composition and a tire comprising the same.
- conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer is polymerized by using a compound represented by the following formula (1) in a solvent to the metal terminal Forming an active polymer having; And (b) adding a compound represented by Formula 2 to the active polymer to modify the conjugated diene-based polymer.
- R is a nitrogen-containing group
- X is a hydrocarbon obtained from polymerization of a conjugated diene monomer or an aromatic vinyl monomer
- n is an integer from 1 to 10
- M is an alkali metal
- 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 an alkyl group having 1 to 10 carbon atoms each independently
- 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.
- a modified conjugated diene-based polymer prepared according to the method for producing the modified conjugated diene-based polymer represented by the following formula (7):
- 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
- 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
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- 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.
- a denaturing agent characterized in that the compound represented by the formula (2):
- 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 an alkyl group having 1 to 10 carbon atoms each independently
- 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.
- a modified conjugated diene-based polymer having excellent exothermicity, tensile strength, abrasion resistance, and wet road resistance can be prepared and used in a rubber composition for a tire.
- a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer is polymerized in a solvent using a compound represented by the following formula (1) to form an active polymer having a metal terminal step; And (b) adding a compound represented by Formula 2 to the active polymer to modify the conjugated diene-based polymer.
- R is a nitrogen-containing group
- X is a hydrocarbon obtained from polymerization of a conjugated diene monomer or an aromatic vinyl monomer
- n is an integer from 1 to 10
- M is an alkali metal
- 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 an alkyl group having 1 to 10 carbon atoms each independently
- 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.
- 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.
- aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, It may be one or more selected from the group consisting of 1-vinyl-5-hexyl naphthalene, and may be styrene or ⁇ -methylstyrene as another example.
- the solvent is not particularly limited as long as it is a solvent that can be applied to homopolymerization or copolymerization of a conjugated diene monomer, 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 compound represented by Chemical Formula 1 may be used in an amount of 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 monomers.
- an optimal conjugated diene-based polymer for preparing a modified conjugated diene-based polymer may be made.
- the molar ratio of the compound represented by Formula 1 and the compound represented by Formula 2 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 a modified reaction of optimum 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 production 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 aromatic vinyl 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 compound represented by Chemical Formula 1.
- block copolymers are generally easy to be produced due to their difference in reaction rate, but when the polar additive is added, the reaction rate of the aromatic vinyl monomer having a slow reaction rate is increased. This has the effect of inducing a microstructure of the corresponding copolymer, for example a random copolymer.
- 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 step (b) may be a step of injecting one or more, or two to three kinds of compounds represented by the formula (8).
- step (b) 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 2 may be represented by, for example, the following Formula 3 or Formula 4:
- a and c are each independently 0, 1, or 2.
- a modified conjugated diene-based polymer prepared according to the above-described method for producing a modified conjugated diene-based polymer.
- the modified conjugated diene-based polymer may be represented by the following formula (7).
- 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
- 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
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 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 at least 10% by weight, preferably at least 15% by weight, more preferably 20 to 70% by weight.
- the vinyl content means the content of a 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 polymer chain represented by P in Formula 7 may be derived from a homopolymer of conjugated diene monomer or a copolymer of conjugated diene monomer and aromatic vinyl monomer.
- the conjugated diene polymer chain alone has an alkali metal terminal obtained by polymerizing a conjugated diene monomer or conjugated diene monomer and an aromatic vinyl monomer in a batch or continuous method in a hydrocarbon solvent in the presence of an organic alkali metal compound.
- Polymers or copolymers may be formed by reaction with silyl groups substituted with one or more alkoxy groups.
- the conjugated diene-based polymer chain is a conjugated diene-based monomer. It may be a polymer chain comprising 0.0001 to 50% by weight, 10 to 40% by weight or 20 to 40% by weight of the aromatic vinyl monomer based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer.
- the polymer chain consisting of the conjugated diene monomer and the aromatic vinyl monomer may be, for example, a random polymer chain.
- conjugated diene monomer and the aromatic vinyl monomer are as described above.
- 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 consumption, 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 (8) or formula (9):
- R 15 , R 16 , R 18 , R 19 , R 22 , R 23 , R 25 , and R 26 are each independently an alkyl group having 1 to 5 carbon atoms
- R 13 , R 14 , R 17 , R 20 , R 21 , and R 24 are each independently an alkylene group having 1 to 5 carbon atoms
- P is a conjugated diene polymer chain
- 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.
- modified conjugated diene-based polymer may be represented by the following formula (10) or formula (11):
- P is a conjugated diene-based polymer chain
- 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.
- the modified conjugated diene-based polymer may be represented by the following formula (12) or formula (13):
- P is a conjugated diene polymer chain.
- the modified conjugated diene-based 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 terminal 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 include, for example, 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 2 to 20 parts by weight and 2 to 20 parts by weight of the silane coupling agent, and the sum of the weights 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. Excellent effect.
- a denaturing agent is provided, which is a compound represented by the following formula (2).
- 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 an alkyl group having 1 to 10 carbon atoms each independently
- 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.
- the compound of Formula 2 may be represented by, for example, the following Formula 3 or Formula 4:
- a and c are each independently 0, 1, or 2.
- the tire or tire tread is manufactured using a rubber composition including a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved workability, 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 for the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- Three reactors were prepared, among which three reactors were used as polymerization reactors and three reactors were modified reactors.
- Styrene, 1,3-butadiene, and normal hexane from which impurities such as moisture were removed were mixed before entering the reactor at a rate of 1.788 kg / h, 4.477 kg / h, and 4.176 kg / h, respectively.
- the resulting mixed solution was continuously fed to a reactor 1, and then 2,2-bis (2-oxoranyl) propane and 3- (Dimethylamino) -1-Prophyllithium- (isoprene) n were respectively added as polar additives.
- g / h, 22.4 mmol / h was supplied to the reactor 1 reactor and the temperature inside the reactor was adjusted to 70 °C.
- the resulting polymer of the first reactor was continuously fed to the top of the second reactor and the temperature was maintained at 85 ° C. to proceed with the polymerization.
- the resulting polymer in the 2nd reactor was continuously fed to the top of the 3rd reactor, and N, N-Bis (triethoxysilyl propyl) aminopropyl-1-imidazole was continuously fed at a rate of 10.9 mmol / h and the modification was carried out. It was.
- a solution containing isopropyl alcohol and an antioxidant (wingstay-K) mixed at 8: 2 was added to the resulting polymer in a three-phase reactor at a rate of 32.5 g / h to terminate the polymerization reaction to obtain a polymer.
- TDAE oil treated distilled aromatic extract having a glass transition temperature in the range of about -44 to about -50 ° C.
- a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 4 mmol of n-butyllithium was added instead of 3- (Dimethylamino) -1-Prophyllithium- (isoprene) n as an initiator in Example 1. Prepared. The analysis results for the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- Example 1 In Example 1, 4 mmol of n-butyllithium was added instead of 3- (Dimethylamino) -1-Prophyllithium- (isoprene) n, and dimethylchlorosilane, a coupling agent, was used instead of N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole.
- a modified conjugated diene-based polymer was prepared in the same manner as in Example 1 except that 1.2 mmol was added. The analysis results for the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- Table 1 shows the analysis results of the most commercially unmodified conjugated diene-based polymer (5025-2HM grade, manufactured by Lanses Irish GmbH).
- RAE oil was used instead of the TDAE oil used in Example 1.
- Example 2 In Example 2, except that 39.57 mmol / h of n-butyllithium was added instead of 3- (Dimethylamino) -1-Prophyllithium- (isoprene) n as an initiator, a modified conjugated diene System-based polymers were prepared. The analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 2 below.
- Table 2 shows the analysis results of the most commercially unmodified conjugated diene-based polymer (5025-2HM grade, manufactured by Lanses Irish GmbH).
- RAE oil was used instead of the TDAE oil used in Example 1.
- 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
- Samples A, B, C, D, E, F, and D shown in Tables 1 and 2 above were used as raw material rubbers, and blended under the mixing conditions shown in Table 3 below to manufacture examples 1 to 2 and comparative preparation examples 1 to 2.
- a conjugated diene-based polymer rubber composition of 5 was prepared.
- the unit of raw material in Table 2 is phr based on 100 parts by weight of rubber.
- the conjugated diene-based polymer rubber composition is kneaded through a total of first stage kneading and second stage kneading.
- the raw rubber (conjugated diene-based polymer), filler, organosilane coupling agent, oil, zincation, stearic acid antioxidant, antioxidant, wax and accelerator are kneaded using a half-variety mixer equipped with a temperature control device. It was. 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.
- Tables 4 and 5 show the physical properties of the vulcanized rubber.
- the tan ⁇ value at 0 ° C. was higher than that of Comparative Preparation Examples 1 to 5, and the modified conjugated diene of the present invention was applied to a tire.
- the polymer rubber composition was included, it was confirmed that the resistance on the wet road surface was high.
- the ⁇ G ′ value was lower than that of Comparative Preparation Examples 1 to 2 at 60 ° C., thereby improving the dispersion of silica.
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Abstract
Description
구분 | 실시예 1 | 비교예 1 | 비교예 2 | 비교예 3 | |
시료 | A | B | C | D | |
개시제(mmol) | n-부틸리튬 | - | 4 | 4 | - |
a* | 4.3 | - | - | - | |
극성첨가제(g) | 0.9 | 0.9 | 0.9 | - | |
변성제(mmol) | b* | 4.3 | 4.3 | - | - |
커플링제 | c* | - | - | 1.2 | - |
무니점도(MV) | 95 | 88 | 64 | 61 | |
TDAE 오일(phr) | - | - | - | RAE 37.5 | |
NMR(%) | SM | 27 | 27 | 27 | 25 |
Vinyl | 43 | 41 | 43 | 49 | |
GPC(x104) | Mn | 41 | 39 | 31 | 39 |
Mw | 59 | 55 | 50 | 69 | |
PDI | 1.4 | 1.4 | 1.2 | 1.8 |
구분 | 실시예 2 | 비교예 4 | 비교예 5 | |
시료 | E | F | D | |
개시제(mmol) | n-부틸리튬 | - | 39.57 | - |
a* | 22.4 | - | - | |
극성첨가제(g/h) | 4.1 | 4.1 | - | |
변성제(mmol) | b* | 10.9 | 10.9 | - |
무니점도(MV) | 86 | 75 | 61 | |
TDAE 오일(phr) | 25 | 25 | RAE 37.5 | |
NMR(%) | SM | 27 | 27 | 25 |
Vinyl | 43 | 43 | 49 | |
GPC(x104) | Mn | 49 | 47 | 39 |
Mw | 119 | 144 | 69 | |
PDI | 2.4 | 3.1 | 1.8 |
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 | 제조예 1 | 비교제조예 1 | 비교제조예 2 | 비교제조예 3 |
시료 | A | B | C | D |
300% 모듈러스(Kgf/㎠) | 141 | 132 | 104 | 98 |
인장강도(Kgf/㎠) | 215 | 213 | 168 | 161 |
Tan δ at 0℃ | 1.008 | 0.967 | 0.542 | 0.647 |
Tan δ at 60℃ | 0.091 | 0.101 | 0.115 | 0.133 |
60℃ ΔG’(페이니효과) | 0.28 | 0.29 | 0.74 | 0.56 |
구분 | 제조예 2 | 비교제조예 4 | 비교제조예 5 |
시료 | E | F | D |
300% 모듈러스(Kgf/㎠) | 135 | 122 | 98 |
인장강도(Kgf/㎠) | 203 | 193 | 161 |
Tan δ at 0℃ | 0.965 | 0.915 | 0.647 |
Tan δ at 60℃ | 0.101 | 0.108 | 0.133 |
60℃ ΔG’(페이니효과) | 0.29 | 0.29 | 0.56 |
Claims (21)
- (a) 공역디엔계 단량체, 또는 공역디엔계 단량체와 방향족 비닐계 단량체를 용매 하에서 하기 화학식 1로 표시되는 화합물을 이용하여 중합시켜 금속 말단을 갖는 활성 중합체를 형성하는 단계; 및(b) 상기 활성 중합체에 하기 화학식 2로 표시되는 화합물을 투입하여 변성시키는 단계를 포함하는 변성 공역디엔계 중합체의 제조방법:[화학식 1]상기 화학식 1에서 R은 질소 함유기이고, X는 공역디엔계 단량체 또는 방향족 비닐계 단량체의 중합으로부터 얻어지는 탄화수소이고, n은 1~10 의 정수이고, M은 알칼리금속이며;[화학식 2]
- 청구항 1에 있어서,상기 화학식 1로 표시되는 화합물은, 상기 단량체 총 100 g을 기준으로 0.01 내지 10 mmol로 사용되는 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법.
- 청구항 1에 있어서,상기 화학식 1로 표시되는 화합물과 상기 화학식 2로 표시되는 화합물의 몰비는 1: 0.1 내지 1: 10인 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법.
- 청구항 1에 있어서,상기 (a) 단계에서 극성첨가제가 더 투입되는 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법.
- 청구항 1에 있어서,상기 극성첨가제는 상기 화학식 1로 표시되는 화합물 총 1 mmol을 기준으로 0.001 내지 10 g으로 투입되는 것을 특징으로 하는 변성 공역디엔계 중합체의 제조방법.
- 청구항 1 내지 청구항 7 중 어느 한 항의 변성 공역디엔계 중합체의 제조방법에 따라 제조되어 하기 화학식 7로 표시되는 변성 공역디엔계 중합체:[화학식 7]상기 화학식 7에서, 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 공역디엔계 중합체 사슬이고, 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.
- 청구항 8에 있어서,상기 화학식 7은 하기 화학식 8 또는 화학식 9로 표시되는 것을 특징으로 하는 변성 공역디엔계 중합체:[화학식 8][화학식 9]상기 화학식 8 및 화학식 9에서, 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 공역디엔계 중합체 사슬이고, 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.
- 청구항 1에 있어서,상기 변성 공역디엔계 중합체는 1,000 내지 2,000,000 g/mol의 수평균분자량(Mn)을 가지는 것을 특징으로 하는 변성 공역디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공역디엔계 중합체는 0.5 내지 10의 분자량 분포(Mw/Mn)를 가지는 것을 특징으로 하는 변성 공역디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공역디엔계 중합체는, 비닐 함량이 10 중량% 이상인 것을 특징으로 하는 변성 공역디엔계 중합체.
- 청구항 8에 있어서,상기 공역디엔계 중합체 사슬은 공역디엔계 단량체의 단독 중합체 또는 공역디엔계 단량체와 방향족 비닐계 단량체의 공중합체로부터 유래된 것을 특징으로 하는 변성 공역디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공역디엔계 중합체는, 공역디엔계 단량체와 방향족 비닐계 단량체를 합한 총 100 중량%를 기준으로 방향족 비닐계 단량체가 0.0001 내지 50 중량%로 포함된 것을 특징으로 하는 변성 공역디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공역디엔계 중합체는 40 이상의 무니점도를 갖는 것을 특징으로 하는 변성 공역디엔계 중합체.
- 청구항 8 내지 청구항 17 중 어느 한 항의 변성 공역디엔계 중합체 100 중량부, 및 무기 충진제 0.1 내지 200 중량부를 포함하는 변성 공역디엔계 중합체 고무 조성물.
- 청구항 18에 있어서,상기 무기 충진제는 실리카계 충진제, 카본 블랙 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 변성 공역디엔계 중합체 고무 조성물.
- 청구항 18의 변성 공역디엔계 중합체 고무 조성물을 포함하는 타이어 또는 타이어 트레드.
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