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WO2016076549A1 - Polymère diène conjugué modifié, procédé de préparation dudit polymère et composition de caoutchouc contenant ce polymère - Google Patents

Polymère diène conjugué modifié, procédé de préparation dudit polymère et composition de caoutchouc contenant ce polymère Download PDF

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Publication number
WO2016076549A1
WO2016076549A1 PCT/KR2015/011230 KR2015011230W WO2016076549A1 WO 2016076549 A1 WO2016076549 A1 WO 2016076549A1 KR 2015011230 W KR2015011230 W KR 2015011230W WO 2016076549 A1 WO2016076549 A1 WO 2016076549A1
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Prior art keywords
conjugated diene
formula
modified conjugated
independently
based polymer
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Ceased
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PCT/KR2015/011230
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English (en)
Korean (ko)
Inventor
이로미
김노마
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Priority claimed from KR1020150140480A external-priority patent/KR101668567B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2016568781A priority Critical patent/JP6307633B2/ja
Priority to EP15859197.4A priority patent/EP3093297B1/fr
Priority to CN201580010973.6A priority patent/CN106068289B/zh
Priority to US15/119,933 priority patent/US9725527B2/en
Publication of WO2016076549A1 publication Critical patent/WO2016076549A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/26—Incorporating metal atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. More specifically, the present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. It relates to a modified conjugated diene-based polymer having a resistance, a preparation method thereof, and a rubber composition comprising 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 is still much room for improvement in terms of physical properties.
  • the problem to be solved by the present invention is to provide a modified conjugated diene-based polymer and a method for producing the same having excellent exothermicity when included in the rubber composition, and exhibits tensile strength, wear resistance, and wet road resistance.
  • Another object of 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 including the same having excellent exothermicity, tensile strength, wear resistance, and wet road resistance including the modified conjugated diene-based polymer.
  • the present invention provides a modified conjugated diene-based polymer represented by the following formula (1):
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms
  • P is a conjugated diene polymer chain
  • n and m are each independently 1 to 10
  • a And b are each independently 0, 1 or 2
  • c and d are each independently 0, 1, 2 or 3
  • c and d cannot both be 0,
  • a + c and b + d are each independently 1, 2 or 3.
  • the present invention comprises the steps of (a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (2) to the active polymer having an alkali metal terminal:
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the present invention provides a modifier represented by the following formula (2).
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the present invention also provides a modified conjugated diene-based polymer rubber composition comprising the modified conjugated diene-based polymer.
  • 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 and exhibiting tensile strength, abrasion resistance, wet road resistance, and the like when blending silica as a reinforcing agent can be prepared and used in a rubber composition for tires.
  • the present invention provides a modified conjugated diene-based polymer represented by Formula 1:
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms
  • P is a conjugated diene polymer chain
  • n and m are each independently 1 to 10
  • a And b are each independently 0, 1 or 2
  • c and d are each independently 0, 1, 2 or 3
  • c and d cannot both be 0,
  • a + c and b + d are each independently 1, 2 or 3.
  • the conjugated diene polymer chain represented by P in Formula 1 may be derived from a homopolymer of conjugated diene monomer or a copolymer of conjugated diene 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 manner in a hydrocarbon solvent in the presence of an organic alkali metal compound.
  • a copolymer may be formed by reaction with a silyl group substituted with one or more alkoxy groups.
  • the conjugated diene-based polymer chain is a conjugated diene-based monomer.
  • the polymer chain may include 0.0001 to 50% by weight, 10 to 40% by weight, or 20 to 40% by weight of the aromatic vinylic monomer based on a total of 100% 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 90, more preferably 50 to 80.
  • the modified conjugated diene-based polymer has, for example, 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, most preferably 100,000 to 500,000 g / mol or 200,000 to 700,000 g / mol.
  • Mn number average molecular weight
  • 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 PDI of 1 to 10, preferably 1 to 5, and more preferably 1 to 2.
  • the compound represented by Chemical Formula 1 may be, for example, a compound represented by Chemical Formula 1a.
  • c and d are each independently 0, 1, 2 or 3, and c and d may not be all 0, and n and m are each independently 1 to 10.
  • the present invention comprises the steps of (a) polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organoalkali metal compound to form an active polymer having an alkali metal terminal; And (b) provides a method for producing a modified conjugated diene-based polymer comprising the step of modifying the compound represented by the formula (2) to the active polymer having an alkali metal terminal:
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the organoalkali metal compound may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyllithium, It may be at least one selected from the group consisting of n-eicosillithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium.
  • the organic alkali metal compound may be n-butyllithium, sec-butyllithium or a mixture thereof.
  • the organoalkali metal compound consists 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 the group, and may also be used in combination with other organic alkali metal compounds.
  • 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 organoalkali metal compound is 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 the total molar ratio of the monomer.
  • the above 'activation molar ratio criteria' means that the organoalkali metal compound used in the present invention may be deactivated depending on the water content, so that the use content is defined based on the activation.
  • an optimal conjugated diene-based polymer for preparing a modified conjugated diene-based polymer can be made.
  • the molar ratio of the organic alkali metal compound and the compound represented by Chemical 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 alkali metal terminal means a polymer in which a polymer anion and an alkali 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 organoalkali metal compound.
  • 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 preparation method of the present invention includes the step of modifying the compound represented by the following formula (2) to the active polymer having the alkali metal terminal.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the compound represented by Chemical Formula 2 may be, for example, a compound represented by Chemical Formula 2a.
  • n and m are each independently 1 to 10.
  • the step (b) may be a step of injecting one or more, or two to three kinds of compounds represented by Formula 1, for example.
  • 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.
  • a denaturing agent is provided, which is a compound represented by the following formula (2).
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, n and m are each independently 1 to 10, a and b are each independently 0, 1 Or two.
  • the compound represented by Formula 2 may be, for example, a compound represented by Formula 2a.
  • n and m are each independently 1 to 10.
  • a modified conjugated diene-based polymer rubber composition comprising 10 to 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of an inorganic filler based on 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 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.
  • 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 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.
  • 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 processability, thereby being excellent in exothermicity, tensile strength, wear resistance, and wet road resistance. It has the advantage of low rolling resistance.
  • the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried by roll to remove residual solvent and water to prepare a modified conjugated diene-based polymer.
  • the analysis results for the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
  • a sample was prepared in the same manner as in Example 1 except that 1.5 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added.
  • a sample was prepared in the same manner as in Example 1 except that 2 g of 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was added.
  • a sample was prepared in the same manner as in Example 1 except that 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine was not added.
  • a sample was prepared in the same manner as in Example 1 except that 1.8 g of 1,4-bis (3- (triethoxysilyl) propyl) piperazine was added.
  • 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 1 Example 2
  • Example 3 Comparative Example 1 Comparative Example 2 sample A B C D E Denaturant a - b Denaturant equivalent eq / [NBL] 0.5 1.0 1.5 - 1.5 Mooney 78 70 69 63 68 Styrene (%) 26 27 27 27 26 vinyl(%) 42 41 42 41 41 GPC ( ⁇ 10 4 ) Mn 40 38 36 34 37 Mw 62 58 50 41 50 PDI 1.6 1.5 1.4 1.2 1.3
  • the conjugated diene-based polymer rubber composition was prepared by blending A to E in the samples shown in Table 1 as raw material rubbers under the blending conditions shown in Table 2 below.
  • the unit of raw material in Table 2 is phr based on 100 parts by weight of rubber.
  • the rubber composition of the conjugated diene-based polymer 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, galvanizing agent, stearic acid antioxidant, antioxidant, wax and accelerator are prepared using a half-variety mixer with temperature control device. 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 3 shows the physical properties of the vulcanized rubber.
  • the tan ⁇ value at 0 ° C. was higher than that of Comparative Preparation Example 2, and the modified conjugated diene-based polymer of the present invention was applied to a tire.
  • the rubber composition is included, it was confirmed that the resistance on the wet road surface was high.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un agent modificateur à structure 1,4-bis (alcoxysilyle alkylène oxyalkylène) pipérazine, un polymère diène conjugué modifié qui est modifié à l'aide dudit agent modificateur, et un procédé de production dudit agent.
PCT/KR2015/011230 2014-11-13 2015-10-22 Polymère diène conjugué modifié, procédé de préparation dudit polymère et composition de caoutchouc contenant ce polymère Ceased WO2016076549A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2016568781A JP6307633B2 (ja) 2014-11-13 2015-10-22 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
EP15859197.4A EP3093297B1 (fr) 2014-11-13 2015-10-22 Polymère diène conjugué modifié, procédé de préparation dudit polymère et composition de caoutchouc contenant ce polymère
CN201580010973.6A CN106068289B (zh) 2014-11-13 2015-10-22 改性共轭二烯聚合物、该聚合物的制备方法以及含有该聚合物的橡胶组合物
US15/119,933 US9725527B2 (en) 2014-11-13 2015-10-22 Modified conjugated diene polymer, method for preparing same, and rubber composition containing same

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KR20140158077 2014-11-13
KR10-2014-0158077 2014-11-13
KR10-2015-0140480 2015-10-06
KR1020150140480A KR101668567B1 (ko) 2014-11-13 2015-10-06 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018531998A (ja) * 2015-12-24 2018-11-01 エルジー・ケム・リミテッド 変性共役ジエン系重合体、その製造方法及び変性剤
JP2019500475A (ja) * 2016-11-23 2019-01-10 エルジー・ケム・リミテッド 変性共役ジエン系重合体およびその製造方法

Citations (5)

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