WO2015072781A1 - Polymère diénique conjugué modifié, procédé de préparation associé et composition de caoutchouc le contenant - Google Patents

Polymère diénique conjugué modifié, procédé de préparation associé et composition de caoutchouc le contenant Download PDF

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WO2015072781A1
WO2015072781A1 PCT/KR2014/010962 KR2014010962W WO2015072781A1 WO 2015072781 A1 WO2015072781 A1 WO 2015072781A1 KR 2014010962 W KR2014010962 W KR 2014010962W WO 2015072781 A1 WO2015072781 A1 WO 2015072781A1
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Prior art keywords
conjugated diene
based polymer
modified conjugated
formula
compound represented
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PCT/KR2014/010962
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English (en)
Korean (ko)
Inventor
최흥열
김노마
김유진
이희승
손기석
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주식회사 엘지화학
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Priority to JP2016529734A priority Critical patent/JP6476179B2/ja
Priority to US14/909,902 priority patent/US9944741B2/en
Priority to CN201480045549.0A priority patent/CN105473624B/zh
Priority to EP14862792.0A priority patent/EP3070105B1/fr
Priority claimed from KR1020140158674A external-priority patent/KR101554363B1/ko
Publication of WO2015072781A1 publication Critical patent/WO2015072781A1/fr

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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
    • 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
    • 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.
  • an object of this invention is to provide the tire containing the said rubber composition.
  • the present invention (a) conjugated diene monomer, or conjugated diene monomer and the aromatic vinyl monomer by polymerization using a compound represented by the following formula (1) in a hydrocarbon solvent having an alkali metal terminal activity Forming a polymer; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of coupling or reacting the active polymer with a compound represented by the formula (2):
  • 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 of 1 to 10
  • M is an alkali metal
  • R 1 is independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • a is an integer of 0 to 2
  • n is an integer of 1 to 3.
  • the present invention provides a modified conjugated diene-based polymer prepared according to the method for producing the modified conjugated diene-based polymer represented by the following formula (3):
  • R 1 is each independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • P is a conjugated diene polymer chain
  • a is 0, 1, or 2
  • b is 1, 2, or 3
  • a + b is 1, 2, or 3
  • n is an integer of 1 to 3.
  • the present invention also provides a modified conjugated diene-based polymer rubber composition comprising a modified conjugated diene-based polymer prepared according to the method for producing the modified conjugated diene-based polymer.
  • the present invention provides a modifier, characterized in that the compound represented by the formula (2):
  • R 1 is independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • a is an integer of 0 to 2
  • n is an integer of 1 to 3.
  • the present invention also provides a tire or tire tread comprising the modified conjugated diene-based polymer rubber composition.
  • 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.
  • Method for producing a modified conjugated diene-based polymer of the present invention is (a) a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer is polymerized using a compound represented by the following formula (1) in a hydrocarbon solvent to the alkali metal terminal Forming an active polymer having; And (b) coupling or reacting the active polymer with a compound represented by Formula 2 below:
  • 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 of 1 to 10
  • M is an alkali metal
  • R 1 is independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • a is an integer of 0-2 and n is an integer of 1-3.
  • the conjugated diene monomer in the present invention is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be one or more selected from the group consisting of butadiene, but is not necessarily limited thereto.
  • the aromatic vinyl monomer is, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) It may be at least one selected from the group consisting of styrene and 1-vinyl-5-hexyl naphthalene, preferably styrene or ⁇ -methylstyrene.
  • the amount of the aromatic vinyl monomer used is 0.0001 to 40% by weight, preferably 10 to 35% by weight, more preferably 20 to 30% by weight, based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer. Can be.
  • the hydrocarbon solvent may be one or more selected from the group consisting of a hydrocarbon or n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene, but is not necessarily limited thereto.
  • the nitrogen-containing group is an amino group
  • Alkylamino groups such as methylamino, dimethylamino, ethylamino, propylamino, butylamino and cyclohexylamino
  • arylamino such as phenylamino, tolylamino and naphthylamino.
  • n is an integer of 1 to 10, and when applied to a tire within this range, it produces an effect of exothermicity, tensile strength, wear resistance and wet road resistance.
  • M may be one selected from the group consisting of lithium, sodium, potassium, rubidium and cesium as alkali metals.
  • the compound represented by Formula 1 may be a compound represented by Formula 4 below:
  • 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 active polymer having the alkali metal terminal means a polymer in which a polymer anion and an alkali metal cation are bonded.
  • Method for producing a modified conjugated diene polymer of the present invention may be carried out by further adding a polar additive during the polymerization of (a) as an example.
  • the polar additive is, for example, a base, and in another example, ether, amine or a mixture thereof, tetrahydrofuran, ditetrahydropripropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl Ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine Selected from the group consisting of ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.
  • the polar additive may be used in an amount of 0.001 to 50 g, preferably 0.001 to 10 g, and more preferably 0.005 to 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, preferably 0.005 to 1 g, more preferably 0.005 to 0.1 g based on a total of 1 mmol of the compound represented by Chemical Formula 1.
  • the polymerization of (a) may be anionic polymerization, for example.
  • the polymerization of (a) may be a living anion polymerization to obtain the active terminal by the growth reaction by the anion.
  • the 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) is, for example, -20 to 200 ° C, preferably 0 ° C to 150 ° C, more preferably 10 to 120 ° C.
  • Step (b) is a step of preparing a modified conjugated diene-based polymer represented by the formula (3) by coupling or reacting the active polymer formed in the step (a) with a compound represented by the formula (2):
  • R 1 is independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • a is an integer of 0-2 and n is an integer of 1-3.
  • the compound represented by Formula 2 may be a compound represented by Formula 5 below:
  • Step (b) is carried out at 0 to 90 °C for 1 minute to 5 hours.
  • the method for producing the modified conjugated diene-based polymer of the present invention may be, for example, a batch or a continuous polymerization method including one or two or more reactors.
  • 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 method for producing the modified conjugated diene-based polymer of the present invention may be, for example, a batch or a continuous polymerization method including one or two or more reactors.
  • the present invention provides a modified conjugated diene-based polymer prepared according to the method for producing the modified conjugated diene-based polymer represented by Formula 3 below:
  • R 1 is each independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • P is a conjugated diene polymer chain
  • a is 0, 1, or 2
  • b is 1, 2, or 3
  • a + b is 1, 2, or 3
  • n is an integer of 1 to 3.
  • the conjugated diene polymer chain represented by P in Formula 3 may be derived from a homopolymer of conjugated diene monomer or a copolymer of conjugated diene monomer and aromatic vinyl monomer.
  • the conjugated diene-based polymer chain is 0.0001 to 40% by weight, preferably 10 to 35% by weight, based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer, more preferably 20 to 30%. It may be a polymer chain comprising a weight percent.
  • the polymer chain consisting of the conjugated diene monomer and the vinyl aromatic monomer may be, for example, a random polymer chain.
  • the modified conjugated diene-based polymer may have a number average molecular weight of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, and more preferably 100,000 to 500,000 g / mol.
  • the modified conjugated diene-based polymer may be, for example, a vinyl content of 18% or more, preferably 25% or more, and more preferably 30 to 70%, and the glass transition temperature of the polymer is increased within this range to be applied to a tire. In addition to satisfying the properties required for tires such as driving resistance and braking force, the fuel consumption is reduced.
  • the vinyl content means the content of the monomer having a vinyl group, or the content of the 1,2-added conjugated diene monomer rather than 1,4-addition based on 100% by weight of the conjugated diene monomer.
  • 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.
  • the modified conjugated diene-based polymer may have a PDI of 0.5 to 10, preferably 0.5 to 5, and more preferably 1.0 to 2.0.
  • the modified conjugated diene-based polymer has a characteristic of viscoelasticity, and when measured at 10 Hz through DMA after silica blending, a Tan ⁇ value at 0 ° C. (Tan ⁇ at 0 ° C.) is 0.6 to 1, or 0.9 to 1, and Compared with the conventional invention within the range, there is an effect that the road surface resistance or wetting resistance is greatly improved.
  • Tan ⁇ value (Tan ⁇ at 60 ° C) at 60 ° C may be, for example, 0.06 to 0.09, or 0.07 to 0.08, and within this range, the rolling resistance or rotational resistance (RR) is greatly improved compared to the conventional invention. Seems.
  • the present invention provides a modifier, characterized in that the compound represented by the formula (2):
  • R 1 is independently an alkyl group or alkylsilyl group having 1 to 8 carbon atoms
  • R 2 is an alkylene group having 1 to 8 carbon atoms
  • R 3 and R 4 are each independently an alkyl group having 1 to 8 carbon atoms.
  • a is an integer of 0-2 and n is an integer of 1-3.
  • the present invention also provides a modified conjugated diene-based polymer rubber composition comprising the modified conjugated diene-based polymer.
  • the modified conjugated diene-based polymer rubber composition 10 to 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of the inorganic filler with respect to 100 parts by weight of the modified conjugated diene-based polymer.
  • 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, for example, carbon black, silica filler, or a mixture thereof.
  • the inorganic filler may be silica, in which case the dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding (sealing) the silica particles to the ends of the modified conjugated diene-based polymer of the present disclosure.
  • the modified conjugated diene-based polymer rubber composition may further include another conjugated diene-based polymer as an example.
  • the other conjugated diene-based polymer may be, for example, 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.
  • the SBR may be, for example, solution styrene-butadiene rubber (SSBR).
  • SSBR solution styrene-butadiene rubber
  • the modified conjugated diene-based polymer rubber composition of the present invention 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.
  • 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 carbon black of 10 to 99% by weight of the modified conjugated diene-based polymer and 1 to 90% by weight of other conjugated diene-based polymer, carbon black It may include 1 to 100 parts by weight, 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 to have excellent processability. It works.
  • the present invention provides a tire or tire tread comprising the rubber composition.
  • 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-propyllithium- (isoprene) 2 were added as polar additives.
  • the reactor was fed to a reactor at a rate of 3.6 g / h and 22.4 mmol / h, respectively, and the reactor internal temperature 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 second stage reactor was continuously fed to the top of the third stage reactor, bis (triethoxysilylpropyl) -N-methylamine was continuously fed at a rate of 10.6 mmol / h and the modification was carried out. .
  • 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.
  • Roll drying was carried out to remove residual solvent and water to prepare a modified conjugated diene polymer.
  • Table 2 The analysis results for the modified conjugated diene-based polymer thus prepared are shown in Table 2 below.
  • 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 as an initiator.
  • 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 Dis GmbH). RAE oil was used for the unmodified conjugated diene-based polymer (TUFDENETM 3835).
  • a modified conjugated diene-based polymer was prepared in the same manner as in Example 2 except that 39.57 mmol / h of n-butyllithium was added as an initiator.
  • 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 TDAE oil.
  • 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, and F 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 prepare Examples 1 to 2 and Comparative Production Examples 1 to 4.
  • a conjugated diene-based polymer rubber composition 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 material rubber (conjugated diene polymer), filler, organosilane coupling agent, oil, zincation, stearic acid antioxidant, antioxidant, wax and accelerator are kneaded by using a half-barrier mixer equipped with a temperature controller. 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 4, and the modified conjugated diene of the present invention was applied to the tire.
  • the polymer rubber composition was included, it was confirmed that the resistance on the wet road surface was high.
  • the ⁇ G 'value is lower than that of Comparative Preparation Examples 1 to 4 at 60 ° C., so that wet road resistance and rolling resistance properties are improved and silica is improved. It was confirmed that the dispersion degree of.

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Abstract

La présente invention concerne un procédé de préparation d'un polymère diénique conjugué modifié, le procédé comprenant les étapes consistant à : (a) polymériser un monomère diénique conjugué, ou un monomère diénique conjugué et un monomère vinylique aromatique, à l'aide d'un composé représenté par la formule chimique 1 en présence d'un solvant hydrocarbure, pour former un polymère actif ayant une terminaison de métal alcalin ; et (b) coupler ou faire réagir le polymère actif avec un composé représenté par la formule chimique 2.
PCT/KR2014/010962 2013-11-15 2014-11-14 Polymère diénique conjugué modifié, procédé de préparation associé et composition de caoutchouc le contenant WO2015072781A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2016529734A JP6476179B2 (ja) 2013-11-15 2014-11-14 変性共役ジエン系重合体、その製造方法、およびこれを含むゴム組成物
US14/909,902 US9944741B2 (en) 2013-11-15 2014-11-14 Modified conjugated diene polymer, method for preparing same, and rubber composition containing same
CN201480045549.0A CN105473624B (zh) 2013-11-15 2014-11-14 改性共轭二烯聚合物及其制备方法，和含有该改性共轭二烯聚合物的橡胶组合物
EP14862792.0A EP3070105B1 (fr) 2013-11-15 2014-11-14 Polymère diénique conjugué modifié, procédé de préparation associé et composition de caoutchouc le contenant

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KR20130138840 2013-11-15
KR10-2013-0138840 2013-11-15
KR1020140158674A KR101554363B1 (ko) 2013-11-15 2014-11-14 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물
KR10-2014-0158674 2014-11-14

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Cited By (1)

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CN110268011A (zh) * 2017-08-24 2019-09-20 Lg化学株式会社 改性聚合引发剂和包括由其衍生的官能团的改性的基于共轭二烯的聚合物

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JP5394877B2 (ja) * 2008-10-16 2014-01-22 住友ゴム工業株式会社 ゴム組成物及びタイヤ
KR20120130253A (ko) * 2010-04-16 2012-11-29 아사히 가세이 케미칼즈 가부시키가이샤 변성 공액 디엔계 중합체의 제조 방법, 변성 공액 디엔계 중합체 및 변성 공액 디엔계 중합체 조성물
JP2013133387A (ja) * 2011-12-26 2013-07-08 Sumitomo Rubber Ind Ltd ゴム組成物及び空気入りタイヤ
JP2013139491A (ja) * 2011-12-28 2013-07-18 Sumitomo Rubber Ind Ltd 共重合体、ゴム組成物及び空気入りタイヤ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110268011A (zh) * 2017-08-24 2019-09-20 Lg化学株式会社 改性聚合引发剂和包括由其衍生的官能团的改性的基于共轭二烯的聚合物
US11254801B2 (en) 2017-08-24 2022-02-22 Lg Chem, Ltd. Modified polymerization initiator and modified conjugated diene- based polymer including functional group derived therefrom

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