WO2016104930A1 - Aminosilane terminal modifier to which functional group has been introduced, method for producing terminal-modified conjugated diene polymer using the aminosilane terminal modifier, and terminal-modified conjugated diene polymer produced according to the method - Google Patents
Aminosilane terminal modifier to which functional group has been introduced, method for producing terminal-modified conjugated diene polymer using the aminosilane terminal modifier, and terminal-modified conjugated diene polymer produced according to the method Download PDFInfo
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- WO2016104930A1 WO2016104930A1 PCT/KR2015/011229 KR2015011229W WO2016104930A1 WO 2016104930 A1 WO2016104930 A1 WO 2016104930A1 KR 2015011229 W KR2015011229 W KR 2015011229W WO 2016104930 A1 WO2016104930 A1 WO 2016104930A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—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
- 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
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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 an aminosilane-based end-modifying agent having a functional group, a method for producing a terminal-modified conjugated diene-based polymer using the same, and a terminal-modified conjugated diene-based polymer prepared accordingly.
- a rubber composition for automobile tires a rubber composition containing a conjugated diene polymer such as polybutadiene, butadiene-styrene polymer, or the like is used.
- the problem to be solved by the present invention is to provide a terminal modifier of the conjugated diene-based polymer for improving the mechanical strength and processability, such as the wear of the conjugated diene-based polymer contained in the rubber composition.
- Another object of the present invention is to provide a method for producing a terminally modified conjugated diene-based polymer using the terminal modifier.
- Another problem to be solved by the present invention is to provide a terminal modified conjugated diene polymer characterized in that the terminal modifier is bonded.
- a terminally modified conjugated diene-based polymer characterized in that the aminosilane-based terminal modifier represented by the following formula (1) is bonded to the terminal of the conjugated diene-based polymer.
- R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element
- R 3 is a hydrocarbon having 1 to 10 carbon atoms
- R 4 and R 5 is carbon It is a hydrocarbon of 1-20
- R ⁇ 6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- a) a step of polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organometallic compound to form an active polymer having an alkali metal terminal.
- a method for producing a terminal modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (1) to the active polymer having an alkali metal terminal.
- R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element
- R 3 is a hydrocarbon having 1 to 10 carbon atoms
- R 4 and R 5 is carbon It is a hydrocarbon of 1-20
- R ⁇ 6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- an aminosilane-based terminal modifier represented by the following formula (1) is provided.
- R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element
- R 3 is a hydrocarbon having 1 to 10 carbon atoms
- R 4 and R 5 is carbon It is a hydrocarbon of 1-20
- R ⁇ 6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- the terminally modified conjugated diene-based polymer is substituted with a group in which the aminosilane end-modifier used comprises a tertiary amine group and a silica affinity group or a hexane affinity group.
- the aminosilane end-modifier used comprises a tertiary amine group and a silica affinity group or a hexane affinity group.
- the aminosilane-based modifying agent of the present invention increases the Mooney viscosity due to hydrolysis and condensation reaction when the number of alkoxy groups reacted with silica to increase the molecular weight and increase the modification rate, the viscosity increases during storage
- the terminal anion reactivity can be further increased to selectively react with the carbonyl group.
- a terminally modified conjugated diene-based polymer characterized in that the aminosilane-based terminal modifier represented by the following formula (1) is bonded to the terminal of the conjugated diene-based polymer.
- R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element
- R 3 is a hydrocarbon having 1 to 10 carbon atoms
- R 4 and R 5 is carbon It is a hydrocarbon of 1-20
- R ⁇ 6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- the hetero element is preferably N, S or O.
- R 1 and R 2 are preferably an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms including a hetero element.
- R 3 is preferably an alkylene group having 1 to 10 carbon atoms.
- R 4 and R 5 are preferably an alkyl group having 1 to 20 carbon atoms.
- R 6 is preferably an alkyl group having 1 to 10 carbon atoms when m is 1. When m is 2, the compound of formula 1 is not substituted with R 6 .
- the terminally 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 2,000,000 g / mol, more preferably 100,000 to 2,000,000 g / mol.
- Mn number average molecular weight
- the terminally modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1.05 to 10, preferably 1.1 to 5, more preferably 1.1 to 4.
- Mw / Mn molecular weight distribution
- the rubber composition may have improved mechanical properties, low fuel consumption properties and wear resistance properties.
- the terminally modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, preferably 10% by weight or more, more preferably 15 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 may be increased to satisfy properties required for the tire such as running resistance and braking force when applied to the tire, as well as fuel. It has the effect of reducing consumption.
- the terminally modified conjugated diene polymer includes 1 to 60 wt%, 10 to 50 wt%, or 15 to 40 wt% of an aromatic vinyl monomer based on a total of 100 wt% of the conjugated diene monomer and the aromatic vinyl monomer. It may comprise a conjugated diene polymer chain which is a polymer chain made.
- the polymer chain 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.
- 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.
- a) a step of polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organometallic compound to form an active polymer having an alkali metal terminal.
- a method for producing a terminal modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (1) to the active polymer having an alkali metal terminal.
- R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element
- R 3 is a hydrocarbon having 1 to 10 carbon atoms
- R 4 and R 5 is carbon It is a hydrocarbon of 1-20
- R ⁇ 6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- conjugated diene monomer and the aromatic vinyl 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 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 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 is 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 from the 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 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 monomers.
- an optimal conjugated diene-based polymer for preparing a terminally modified conjugated diene-based polymer can be made.
- the molar ratio of the organometallic compound and the compound represented by Formula 1 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 method of preparing the terminally modified conjugated diene-based polymer may be carried out by further adding a polar additive during 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 organometallic compound introduced.
- block polymers are generally easy to be produced due to their reaction rate difference, but when the polar additive is added, the reaction rate of the aromatic vinyl monomer having a slow reaction rate is increased. There is an effect of inducing a microstructure of the corresponding polymer, for example a random polymer.
- the polymerization of a) may be, for example, anionic polymerization, and specifically, the polymerization of a) may be a living anion polymerization obtained by obtaining an active terminal by a 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 increasing the reaction temperature by adding heat after the addition of the organometallic compound, and the constant temperature polymerization means a polymerization method in which no heat is optionally added after the addition of 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.
- Step b) may be a step of injecting one or more, or two to three kinds of compounds represented by the formula (1).
- step b) may be a step of reacting for 1 minute to 5 hours at 0 to 90 °C, for example.
- the method for producing the terminally modified conjugated diene-based polymer may be, for example, a batch polymerization method or a continuous polymerization method including one or more reactors.
- an aminosilane-based terminal modifier represented by the following formula (1) is provided.
- R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element
- R 3 is a hydrocarbon having 1 to 10 carbon atoms
- R 4 and R 5 is carbon It is a hydrocarbon of 1-20
- R ⁇ 6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- the hetero element is preferably N, S or O.
- R 1 and R 2 are preferably an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms including a hetero element.
- R 3 is preferably an alkylene group having 1 to 10 carbon atoms.
- R 4 and R 5 are preferably an alkyl group having 1 to 20 carbon atoms.
- R 6 is preferably an alkyl group having 1 to 10 carbon atoms when m is 1. When m is 2, the compound of formula 1 is not substituted with R 6 .
- the terminal modification agent according to the present invention is an aminosilane-based terminal modification agent wherein the aminosilane derivative is substituted with a group containing a tertiary amine group, a silica affinity group such as ethylene glycol group, or a hexane affinity group such as alkyl group or aryl group.
- a tertiary amine group such as ethylene glycol group
- a hexane affinity group such as alkyl group or aryl group.
- the tertiary amine groups in the terminal modifiers enhance the dispersion of the silica and serve as catalysts in the reaction
- the silica affinity group serves to react with the silica to improve the wear and processability of the polymer.
- Modifiers comprising hexane affinity groups can also increase the polymer's solubility in hexanes to increase the polymer's denaturation rate.
- Formula 1 may be represented by the following Formula 1a.
- styrene, 710 g of 1,3 butadiene, 5 kg of normal hexane and 1.1 g of DTP (2,2-di (2-tetrahydrofuryl) propane) were added to a 20 L autoclave reactor, and the temperature of the reactor was raised to 40 ° C. It was. When the temperature inside the reactor reached 40 ° C, 29.3 g (2.62 wt% in hexane, 33% activation) of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. After 30 minutes, 20 g of 1,3-butadiene was added to cap the SSBR end with butadiene.
- a terminally modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that ethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate was used as the terminal modifier.
- Comparative Example 1 (combination of polymer components) using ethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate when polymerization was carried out with the terminal denaturant of Example 1 according to the present invention
- the binding efficiency of the polymer component was increased (63%) rather than the efficiency (60%). This is the result of increasing the reactivity with the terminal anion when one ester group having a high reactivity of the rubber terminal anion is increased, thereby producing a highly modified polymer.
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Abstract
Description
구분 | GPC(×104) | |||||
Mn | Mw | Mp | 결합효율 | 분자량 분포(Mw/Mn) | ||
(%) | ||||||
실시예 1 | 33 | 49 | Mp1 | 25 | 37 | 1.5 |
Mp2 | 58 | 24 | ||||
Mp3 | 87 | 39 | ||||
비교예 1 | 41 | 62 | Mp1 | 28 | 40 | 1.5 |
Mp2 | 62 | 60 |
division | GPC (× 10 4 ) | |||||
Mn | Mw | Mp | Coupling efficiency | Molecular Weight Distribution (Mw / Mn) | ||
(%) | ||||||
Example 1 | 33 | 49 | Mp1 | 25 | 37 | 1.5 |
Mp2 | 58 | 24 | ||||
Mp3 | 87 | 39 | ||||
Comparative Example 1 | 41 | 62 | Mp1 | 28 | 40 | 1.5 |
Mp2 | 62 | 60 |
Claims (12)
- 공역디엔계 중합체 말단에 하기 화학식 1로 표시되는 아미노실란계 말단변성제가 결합되어 있는 것을 특징으로 하는 말단변성 공역디엔계 중합체: A terminal-modified conjugated diene-based polymer, characterized in that the aminosilane-based terminal modifier represented by the formula (1) is bonded to the terminal of the conjugated diene-based polymer:[화학식 1][Formula 1]상기 화학식 1에서, R1 및 R2 는 탄소수 1~20의 탄화수소, 또는 헤테로 원소를 포함하는 탄소수 1~20의 탄화수소이고, R3는 탄소수 1~10의 탄화수소이고, R4 및 R5 는 탄소수 1~20의 탄화수소이고, R6는 m이 1일 경우에 탄소수 1~10의 탄화수소이고, n은 1~3의 정수이고, m은 1~2의 정수이다.In Formula 1, R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element, R 3 is a hydrocarbon having 1 to 10 carbon atoms, R 4 and R 5 is carbon It is a hydrocarbon of 1-20, R <6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- 청구항 1에 있어서,The method according to claim 1,상기 말단변성 공역디엔계 중합체는 1,000 내지 2,000,000 g/mol의 수평균분자량(Mn)을 가지는 것을 특징으로 하는 말단변성 공역디엔계 중합체.The terminally modified conjugated diene-based polymer is a terminally modified conjugated diene-based polymer, characterized in that it has a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol.
- 청구항 1에 있어서,The method according to claim 1,상기 말단변성 공역디엔계 중합체는, 공역디엔계 단량체와 방향족 비닐계 단량체를 합한 총 100 중량%를 기준으로 방향족 비닐계 단량체가 1 내지 60 중량%로 포함된 것을 특징으로 하는 말단변성 공역디엔계 중합체.The terminally modified conjugated diene-based polymer is a terminally modified conjugated diene-based polymer comprising 1 to 60% by weight of an aromatic vinyl monomer based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer. .
- a) 유기 금속 화합물의 존재 하에 탄화수소 용매 중에서 공역디엔계 단량체, 또는 공역디엔계 단량체와 방향족 비닐계 단량체를 중합시켜 알칼리 금속 말단을 갖는 활성 중합체를 형성하는 단계; 및a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organometallic compound to form an active polymer having alkali metal ends; Andb) 상기 알칼리 금속 말단을 갖는 활성 중합체에 하기 화학식 1로 표시되는 화합물을 투입하여 변성시키는 단계를 포함하는 말단변성 공역디엔계 중합체의 제조방법:b) a method of producing a terminal-modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (1) to the active polymer having an alkali metal terminal:[화학식 1][Formula 1]상기 화학식 1에서, R1 및 R2 는 탄소수 1~20의 탄화수소, 또는 헤테로 원소를 포함하는 탄소수 1~20의 탄화수소이고, R3는 탄소수 1~10의 탄화수소이고, R4 및 R5 는 탄소수 1~20의 탄화수소이고, R6는 m이 1일 경우에 탄소수 1~10의 탄화수소이고, n은 1~3의 정수이고, m은 1~2의 정수이다.In Formula 1, R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element, R 3 is a hydrocarbon having 1 to 10 carbon atoms, R 4 and R 5 is carbon It is a hydrocarbon of 1-20, R <6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
- 청구항 5에 있어서,The method according to claim 5,상기 유기 금속 화합물은, 상기 단량체 총 100 g을 기준으로 0.01 내지 10 mmol로 사용되는 것을 특징으로 하는 말단변성 공역디엔계 중합체의 제조방법. The organometallic compound is a method of producing a terminal-modified conjugated diene polymer, characterized in that used in 0.01 to 10 mmol based on a total of 100 g of the monomer.
- 청구항 5에 있어서,The method according to claim 5,상기 유기 금속 화합물과 상기 화학식 1로 표시되는 화합물의 몰비는 1: 0.1 내지 1: 10인 것을 특징으로 하는 말단변성 공역디엔계 중합체의 제조방법. The molar ratio of the organometallic compound and the compound represented by the formula (1) is 1: 0.1 to 1: 10 method for producing a terminal modified conjugated diene polymer.
- 청구항 5에 있어서,The method according to claim 5,상기 a) 단계에서 극성첨가제가 더 투입되는 것을 특징으로 하는 말단변성 공역디엔계 중합체의 제조방법.Method of producing a terminal modified conjugated diene-based polymer, characterized in that the polar additive is further added in step a).
- 청구항 9에 있어서,The method according to claim 9,상기 극성첨가제는 상기 유기금속 화합물 총 1 mmol을 기준으로 0.001 내지 10 g으로 투입되는 것을 특징으로 하는 말단변성 공역디엔계 중합체의 제조방법.The polar additive is prepared from 0.001 to 10 g based on 1 mmol of the total organometallic compound.
- 하기 화학식 1로 표시되는 아미노실란계 말단변성제:An aminosilane-based terminal modifier represented by the general formula (1):[화학식 1][Formula 1]상기 화학식 1에서, R1 및 R2 는 탄소수 1~20의 탄화수소, 또는 헤테로 원소를 포함하는 탄소수 1~20의 탄화수소이고, R3는 탄소수 1~10의 탄화수소이고, R4 및 R5 는 탄소수 1~20의 탄화수소이고, R6는 m이 1일 경우에 탄소수 1~10의 탄화수소이고, n은 1~3의 정수이고, m은 1~2의 정수이다.In Formula 1, R 1 and R 2 is a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms containing a hetero element, R 3 is a hydrocarbon having 1 to 10 carbon atoms, R 4 and R 5 is carbon It is a hydrocarbon of 1-20, R <6> is a C1-C10 hydrocarbon when m is 1, n is an integer of 1-3, m is an integer of 1-2.
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