[go: up one dir, main page]

WO2016093496A1 - Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation du polymère de diène conjugué modifié - Google Patents

Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation du polymère de diène conjugué modifié Download PDF

Info

Publication number
WO2016093496A1
WO2016093496A1 PCT/KR2015/011719 KR2015011719W WO2016093496A1 WO 2016093496 A1 WO2016093496 A1 WO 2016093496A1 KR 2015011719 W KR2015011719 W KR 2015011719W WO 2016093496 A1 WO2016093496 A1 WO 2016093496A1
Authority
WO
WIPO (PCT)
Prior art keywords
conjugated diene
formula
modified conjugated
based polymer
compound represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2015/011719
Other languages
English (en)
Korean (ko)
Inventor
손해성
김노마
이희승
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150143460A external-priority patent/KR101653574B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2016554594A priority Critical patent/JP6552514B2/ja
Priority to CN201580011397.7A priority patent/CN106068286B/zh
Priority to US15/121,804 priority patent/US10118974B2/en
Priority to EP15868082.7A priority patent/EP3101036B1/fr
Publication of WO2016093496A1 publication Critical patent/WO2016093496A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C08C19/22—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
    • 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
    • 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
    • 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, to a modified conjugated diene-based polymer having tensile strength, abrasion resistance, and wet road resistance while having excellent rolling resistance characteristics, It relates to a modified conjugated diene-based polymer prepared, and a rubber composition comprising the same.
  • a rubber composition for automobile tires a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer is used.
  • an object of the present invention is to provide a method for producing a modified conjugated diene polymer having not only excellent rolling resistance properties, but also tensile strength, wear resistance, and wet road resistance.
  • 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) coupling or coupling the active polymer having an alkali metal terminal with a compound represented by the following Chemical Formula 1 to prepare a modified conjugated diene-based polymer represented by the following Chemical Formula 2.
  • a compound represented by the following Chemical Formula 1 to prepare a modified conjugated diene-based polymer represented by the following Chemical Formula 2.
  • R 1 is Or an alkyl group having 1 to 50 carbon atoms, n is 1 to 20, and m is 0 to 20;
  • R 2 is Or an alkyl group having 1 to 50 carbon atoms
  • Pn and Pm are polymers having a number average molecular weight of 1,000 to 100,000,000 g / mol mainly composed of a conjugated diene monomer and a conjugated aromatic monomer, and an acrylic, amine, ether or thioether monomer. It may include, Pn and Pm may be the same or different from each other, a is 1 to 3, b is 0 to 3, n is 1 to 20, m is 0 to 20.
  • the present invention provides a modified conjugated diene-based polymer represented by the following formula (2).
  • R 2 is Or an alkyl group having 1 to 50 carbon atoms
  • Pn and Pm are polymers having a number average molecular weight of 1,000 to 100,000,000 g / mol mainly composed of a conjugated diene monomer and a conjugated aromatic monomer, and an acrylic, amine, ether or thioether monomer. It may include, Pn and Pm may be the same or different from each other, a is 1 to 3, b is 0 to 3, n is 1 to 20, m is 0 to 20.
  • the present invention provides a modifier, characterized in that the compound represented by the formula (1):
  • R 1 is Or it is a C1-C50 alkyl group, n is 1-20, m is 0-20.
  • 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 rolling resistance and at the same time 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 polymer of the present invention is a) polymerizing a conjugated diene monomer or 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. Doing; And b) preparing a modified conjugated diene-based polymer represented by the following Chemical Formula 2 by coupling or combining the active polymer having the alkali metal terminal with a compound represented by the following Chemical Formula 1.
  • R 1 is Or an alkyl group having 1 to 50 carbon atoms, n is 1 to 20, and m is 0 to 20;
  • R 2 is Or an alkyl group having 1 to 50 carbon atoms
  • Pn and Pm are polymers having a number average molecular weight of 1,000 to 100,000,000 g / mol mainly composed of a conjugated diene monomer and a conjugated aromatic monomer, and an acrylic, amine, ether or thioether monomer. It may include, Pn and Pm may be the same or different from each other, a is 1 to 3, b is 0 to 3, n is 1 to 20, m is 0 to 20.
  • the said organic alkali metal compound is an organolithium compound as an anionic polymerization initiator.
  • the organolithium may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyllithium, n- It may be at least one member selected from the group consisting of eicosillithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptelcyclohexyllithium and 4-cyclopentyllithium.
  • the organic alkali metal compound may be, for example, 0.01 to 10 mmol, 0.05 to 5 mmol, 0.3 to 5 mmol, 0.1 to 2 mmol, or 0.15 to 0.8 mmol, based on 100 g of the total monomer.
  • the molar ratio of the organic alkali metal compound and the compound represented by Formula 1 or the compound or polymer represented by Formula 2 is, for example, 1: 0.1 to 1:10, or 1: 0.5 to 1: 2.
  • 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 conjugated diene-based monomer may include 60 to 100% by weight, preferably 60 to 85% by weight, based on a total of 100% by weight of the conjugated diene-based monomer and the aromatic vinyl monomer. Preferably 60 to 80% by weight.
  • the conjugated diene monomer comprises 100 wt% based on a total of 100 wt% of the conjugated diene monomer and the aromatic vinyl monomer in total
  • the polymerization reaction is performed using only the conjugated diene monomer without the aromatic vinyl monomer. To form.
  • 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 aromatic vinyl monomer may include 0 to 40% by weight, preferably 15 to 40% by weight, based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer. Preferably it may comprise 20 to 40% by weight.
  • the vinyl aromatic monomer contains 0 wt% based on a total of 100 wt% of the conjugated diene monomer and the aromatic vinyl monomer, the polymerization reaction is performed using only the conjugated diene monomer without the aromatic vinyl monomer to form an active polymer. It shows.
  • the polymer may include a small amount of acrylic, amine, ether, thioether, or silane monomers, and the small amount of monomers may include 0 to 10 wt% based on a total of 100 wt% of the total monomers. And, it may preferably comprise 0 to 1% by weight.
  • 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 polymerization of step a) may be anionic polymerization, for example.
  • the polymerization of step a) may be a living anion polymerization to obtain the active terminal by the growth reaction by the anion.
  • the polymerization of step 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 step a) is, for example, -20 to 200 ° C, preferably 0 ° C to 150 ° C, more preferably 10 to 120 ° C.
  • 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-based polymer of the present invention may include a step of polymerization by further adding a polar additive during the polymerization of a).
  • 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 organoalkali metal compound to be added.
  • step b The active polymer having an alkali metal end of step a) is coupled or combined with a compound represented by the following formula (1) in step b).
  • R 1 is Or it is a C1-C50 alkyl group, n is 1-20, m is 0-20.
  • the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1a.
  • the compound represented by Chemical Formula 1 is used in an amount of 0.01 to 10 mmol, preferably 0.05 to 5 mmol, more preferably 0.1 to 2 mmol, based on 100 g of the monomers, for example.
  • step b) a modified conjugated diene-based polymer in which a compound represented by the compound represented by Formula 1 is bonded to a chain terminal of the active polymer having an alkali metal end is prepared.
  • the modified conjugated diene-based polymer is a compound represented by the following formula (2).
  • R 2 is Or an alkyl group having 1 to 50 carbon atoms
  • Pn and Pm are polymers having a number average molecular weight of 1,000 to 100,000,000 g / mol mainly composed of a conjugated diene monomer and a conjugated aromatic monomer, and an acrylic, amine, ether or thioether monomer. It may include, Pn and Pm may be the same or different from each other, a is 1 to 3, b is 0 to 3, n is 1 to 20, m is 0 to 20.
  • the compound represented by Formula 2 is a conjugated diene-based polymer using the compound represented by Formula 1, and has a structure in which one or more conjugated diene-based polymerization terminals are bonded to the silane group of Formula 1.
  • the compound represented by Formula 2 may be a compound represented by Formula 2a.
  • a1 to a8 are each 10 to 100,000.
  • 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 present invention also provides a modified conjugated diene-based polymer represented by the following formula (2):
  • R 2 is Or an alkyl group having 1 to 50 carbon atoms
  • Pn and Pm are polymers having a number average molecular weight of 1,000 to 100,000,000 g / mol mainly composed of a conjugated diene monomer and a conjugated aromatic monomer, and an acrylic, amine, ether or thioether monomer. It may include, Pn and Pm may be the same or different from each other, a is 1 to 3, b is 0 to 3, n is 1 to 20, m is 0 to 20.
  • modified conjugated diene-based polymer represented by Formula 2 may be a modified conjugated diene-based polymer represented by the formula (2a).
  • a1 to a8 are each 10 to 100,000.
  • the modified conjugated diene polymer may be, for example, a conjugated diene monomer alone or a chain composed of a conjugated diene monomer and an aromatic vinyl monomer.
  • the chain consisting of the conjugated diene monomer and the aromatic vinyl monomer is 0.0001 to 40% by weight of the aromatic vinyl monomer, preferably 10 to 35 weight based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer. More preferably, it may be a polymer chain including 20 to 30% by weight.
  • the polymer chain consisting of the conjugated diene monomer and the aromatic vinyl monomer may be, for example, a random polymer chain.
  • the modified conjugated diene-based polymer may have a Mooney viscosity of 20 or more, preferably 20 to 150, more preferably 40 to 100.
  • the modified conjugated diene-based polymer may have a number average molecular weight of 1,000 to 10,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 100,000 to 500,000 g / mol.
  • the modified conjugated diene-based polymer may be, for example, a vinyl content of 10% or more, preferably 25% or more, 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 3.
  • 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 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 (1):
  • R 1 is Or it is a C1-C50 alkyl group, n is 1-20, m is 0-20.
  • the denaturant characterized in that the compound represented by Formula 1 may be a denaturant represented by the formula (1a).
  • 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 modified conjugated diene-based polymer rubber composition of the present invention is characterized in that it comprises 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. There is.
  • 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 be made of, 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 with respect to 100 parts by weight of the conjugated diene polymer, and exhibits good physical properties within this range, and further softens the rubber composition to have excellent processability. There is.
  • the present invention also provides a tire or tire tread comprising the modified conjugated diene-based polymer rubber composition.
  • the tire or tire tread is manufactured using a rubber composition comprising a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved processability, thereby providing excellent rolling strength, wear resistance, and wet road resistance. It has the advantage of low resistance.
  • the temperature of the first reactor was maintained at 55 °C, the residence time was 10 minutes.
  • Transfer of the polymer from the first reactor to the second reactor was carried out using a gear pump, the temperature in the second reactor was 58 °C, the residence time was 10 minutes.
  • Polymer transfer from the second reactor to the third reactor was carried out using a gear pump, at which time an additional 60 wt% of 1,3-butadiene solution was injected at a rate of 45.3 g / h.
  • the temperature of the third reactor was maintained at 70 ° C. and the residence time was 40 minutes.
  • Transfer of the polymer from the third reactor to the fourth reactor was carried out using a gear pump, where N, N'-bis (3-trioxazasilabicyclyldecylpropyl) piperazine was added to 3 wt% in normal hexane as a modifier.
  • the diluted solution was injected at a rate of 25.0 g / h.
  • the temperature of the fourth reactor was maintained at 65 ° C., and the residence time was 30 minutes.
  • the polymerization reaction was terminated by injecting a 20 wt% normal hexane solution of wingtay, a polymerization terminator, at a rate of 18.8 g / h into the polymerization solution from the fourth reactor.
  • the polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in a roll to remove the residual solvent and water to prepare a modified conjugated diene-based polymer (A).
  • Example 2 As a denaturant, the same method as in Example 1 except that a 3 wt% normal hexane solution of N, N'-bis (3-trioxazasilabicycleddecylpropyl) piperazine was injected at a rate of 38.8 g / h. As a result, a modified conjugated diene-based polymer (B) was produced.
  • tetrachlorosilane was diluted to 0.5 wt% in normal hexane and injected at a rate of 25.5 g / h, to prepare an unmodified conjugated diene polymer (E) in the same manner as in Example 1. .
  • Transfer of the polymer from the first reactor to the second reactor was carried out using a gear pump, the temperature in the second reactor was 58 °C, the residence time was 10 minutes.
  • Polymer transfer from the second reactor to the third reactor was carried out using a gear pump, at which time an additional 60 wt% of 1,3-butadiene solution was injected at a rate of 45.3 g / h.
  • the temperature of the second reactor was maintained at 70 ° C. and the residence time was 40 minutes.
  • the polymerization reaction was stopped by injecting a wing stay solution, a polymerization terminator, into the polymerization solution from the third reactor.
  • the polymer was put in hot water heated with steam, stirred to remove the solvent, and then dried in a roll to remove the residual solvent and water to prepare a modified conjugated diene-based polymer (F).
  • Mooney Viscosity Using MV-2000 of ALPHA Technologies, preheated for 1 minute using two or more specimens weighing 15g and measured for 4 minutes at 100 °C.
  • the column was a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories, and all of the newly replaced columns were mixed bed type columns.
  • PS polystyrene
  • a raw material rubber conjugated diene polymer
  • a filler As a kneading method of the rubber composition of the conjugated diene polymer, a raw material rubber (conjugated diene polymer), a filler, and an organosilane coupling agent are used under the conditions of 80 rpm in the kneading of the first stage using a half-barrier mixer equipped with a temperature controller. , Oils, zincated, stearic acid antioxidants, antioxidants, waxes and accelerators were kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at the discharge temperature of 140-150 degreeC.
  • Mooney viscosity using MV-2000 of ALPHA Technologies, preheated for 1 minute using two or more specimens weighing 15g and measured for 4 minutes at 100 °C.
  • the rolling resistance (RR) and wet grip of rubber were measured using DMTS (Dynamic Mechanical Thermal Spectrometry; GABO, EPLEXOR 500N). Test conditions were measured as Frequency: 10Hz, Strain (Static strain: 3%, Dynamic strain: 0.25%), Temperature: -60 ⁇ 70 °C. At this time, the rolling resistance is better the lower the Tan ⁇ value measured at 60 °C, the braking resistance is higher the higher the Tan ⁇ value measured at 0 °C. This value was compared to index based on the value of Preparation Example 5, indicating that the larger the index value is excellent.
  • DMTS Dynamic Mechanical Thermal Spectrometry
  • the modified conjugated diene-based polymer rubber compositions of Preparation Examples 1-4 according to the present invention is 300% modulus (tensile stress), tensile strength compared to the unmodified conjugated diene rubber compositions of Preparation Examples 5,6
  • the intensity was above the equivalent.
  • Tan ⁇ at 0 ° C. was improved by 6 to 12%
  • Tan ⁇ at 60 ° C. was improved by 16 to 20%.

Landscapes

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

Abstract

La présente invention concerne un modificateur représenté par la formule chimique 1, un polymère de diène conjugué modifié se liant à celui-ci, et un procédé de préparation de ceux-ci.
PCT/KR2015/011719 2014-12-11 2015-11-03 Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation du polymère de diène conjugué modifié Ceased WO2016093496A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2016554594A JP6552514B2 (ja) 2014-12-11 2015-11-03 変性共役ジエン系重合体、これを含む変性ゴム組成物および変性共役ジエン系重合体の製造方法
CN201580011397.7A CN106068286B (zh) 2014-12-11 2015-11-03 改性共轭二烯聚合物，包含其的改性橡胶组合物，以及制备该改性共轭二烯聚合物的方法
US15/121,804 US10118974B2 (en) 2014-12-11 2015-11-03 Modified conjugated diene polymer, a modified rubber composition containing same, and method for preparing modified conjugated diene polymer
EP15868082.7A EP3101036B1 (fr) 2014-12-11 2015-11-03 Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation du polymère de diène conjugué modifié

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0178302 2014-12-11
KR20140178302 2014-12-11
KR10-2015-0143460 2015-10-14
KR1020150143460A KR101653574B1 (ko) 2014-12-11 2015-10-14 변성 공역디엔계 중합체, 이를 포함하는 변성 고무 조성물 및 변성 공역디엔계 중합체의 제조방법

Publications (1)

Publication Number Publication Date
WO2016093496A1 true WO2016093496A1 (fr) 2016-06-16

Family

ID=56107639

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/011719 Ceased WO2016093496A1 (fr) 2014-12-11 2015-11-03 Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation du polymère de diène conjugué modifié

Country Status (1)

Country Link
WO (1) WO2016093496A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190256635A1 (en) 2017-01-03 2019-08-22 Lg Chem, Ltd. Method for Preparing Modified Conjugated Diene-based Polymer
CN110382566A (zh) * 2017-01-03 2019-10-25 株式会社Lg化学 改性共轭二烯类聚合物和包含其的橡胶组合物
JP2020504212A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP2020504210A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP2020504213A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040312A1 (fr) * 2009-10-02 2011-04-07 旭化成ケミカルズ株式会社 Procédé de production d'un polymère de diène conjugué modifié, polymère de diène conjugué modifié, et composition de polymère de diène conjugué modifié
JP2013010817A (ja) * 2011-06-28 2013-01-17 Sumitomo Rubber Ind Ltd ゴム組成物及び空気入りタイヤ
JP2013082841A (ja) * 2011-10-12 2013-05-09 Asahi Kasei Chemicals Corp 変性共役ジエン系重合体、その製造方法、変性共役ジエン系重合体組成物、及びタイヤ
JP5535877B2 (ja) * 2010-11-10 2014-07-02 日本エラストマー株式会社 変性共役ジエン系共重合体、その製造方法、及び変性共役ジエン系共重合体組成物
WO2014133096A1 (fr) * 2013-02-28 2014-09-04 Jsr株式会社 Polymère de diène conjugué modifié et son procédé de production, composition polymère, polymère réticulé, et pneu
JP2014177517A (ja) * 2013-03-13 2014-09-25 Asahi Kasei Chemicals Corp 変性共役ジエン系重合体組成物、トレッド、サイドウォール及びタイヤ
JP2014177519A (ja) * 2013-03-13 2014-09-25 Asahi Kasei Chemicals Corp 変性共役ジエン系重合体組成物、トレッド、サイドウォール及びタイヤ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040312A1 (fr) * 2009-10-02 2011-04-07 旭化成ケミカルズ株式会社 Procédé de production d'un polymère de diène conjugué modifié, polymère de diène conjugué modifié, et composition de polymère de diène conjugué modifié
JP5535877B2 (ja) * 2010-11-10 2014-07-02 日本エラストマー株式会社 変性共役ジエン系共重合体、その製造方法、及び変性共役ジエン系共重合体組成物
JP2013010817A (ja) * 2011-06-28 2013-01-17 Sumitomo Rubber Ind Ltd ゴム組成物及び空気入りタイヤ
JP2013082841A (ja) * 2011-10-12 2013-05-09 Asahi Kasei Chemicals Corp 変性共役ジエン系重合体、その製造方法、変性共役ジエン系重合体組成物、及びタイヤ
WO2014133096A1 (fr) * 2013-02-28 2014-09-04 Jsr株式会社 Polymère de diène conjugué modifié et son procédé de production, composition polymère, polymère réticulé, et pneu
JP2014177517A (ja) * 2013-03-13 2014-09-25 Asahi Kasei Chemicals Corp 変性共役ジエン系重合体組成物、トレッド、サイドウォール及びタイヤ
JP2014177519A (ja) * 2013-03-13 2014-09-25 Asahi Kasei Chemicals Corp 変性共役ジエン系重合体組成物、トレッド、サイドウォール及びタイヤ

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190256635A1 (en) 2017-01-03 2019-08-22 Lg Chem, Ltd. Method for Preparing Modified Conjugated Diene-based Polymer
CN110382566A (zh) * 2017-01-03 2019-10-25 株式会社Lg化学 改性共轭二烯类聚合物和包含其的橡胶组合物
JP2019534373A (ja) * 2017-01-03 2019-11-28 エルジー・ケム・リミテッド 変性共役ジエン系重合体の製造方法
JP2020504212A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP2020504210A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP2020504211A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP2020504213A (ja) * 2017-01-03 2020-02-06 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
US10920004B2 (en) 2017-01-03 2021-02-16 Lg Chem, Ltd. Method for preparing modified conjugated diene-based polymer
US11001661B2 (en) 2017-01-03 2021-05-11 Lg Chem, Ltd. Modified conjugated diene-based polymer and rubber composition including the same
US11254755B2 (en) 2017-01-03 2022-02-22 Lg Chem, Ltd. Modified conjugated diene-based polymer and rubber composition including the same
US11339238B2 (en) 2017-01-03 2022-05-24 Lg Chem, Ltd. Modified conjugated diene-based polymer and rubber composition including the same
US11427668B2 (en) 2017-01-03 2022-08-30 Lg Chem, Ltd. Modified conjugated diene-based polymer and rubber composition including the same
JP7225100B2 (ja) 2017-01-03 2023-02-20 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP7225102B2 (ja) 2017-01-03 2023-02-20 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP7225101B2 (ja) 2017-01-03 2023-02-20 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物
JP7227136B2 (ja) 2017-01-03 2023-02-21 エルジー・ケム・リミテッド 変性共役ジエン系重合体、およびそれを含むゴム組成物

Similar Documents

Publication Publication Date Title
WO2013119006A1 (fr) Polymère de diène conjugué modifié et procédé pour sa production
WO2015016405A1 (fr) Polymère à base d'un diène conjugué modifié et son procédé de préparation
WO2015034110A1 (fr) Polymère diénique conjugué modifié, procédé pour la préparation d'un polymère diénique conjugué modifié, et composition de caoutchouc contenant le polymère diénique conjugué modifié
WO2018030645A1 (fr) Polymère diénique conjugué modifié, procédé pour sa préparation et composition à base de caoutchouc le contenant
WO2015056898A1 (fr) Polymère à base de diène conjugué modifié, son procédé de préparation, et composition de caoutchouc comprenant celui-ci
WO2017191921A1 (fr) Agent de modification et polymère à base de diène conjugué modifié produit à l'aide de celui-ci
WO2016204575A1 (fr) Procédé de préparation d'une composition de caoutchouc à l'aide d'un agent de modification terminal à base d'aminosilane dans lequel est introduit un groupe fonctionnel et composition de caoutchouc préparé par ce procédé
WO2016104987A1 (fr) Polymère à base de diène conjugué modifié et composition en contenant
WO2017217720A1 (fr) Procédé de préparation d'un polymère à base de diène conjugué modifié, et polymère à base de diène conjugué modifié préparé à l'aide du procédé de préparation
WO2014175561A1 (fr) Procédé de préparation d'un polymère à base de diènes conjugués, composition contenant un polymère et pneu comprenant la composition
WO2015194786A1 (fr) Polymère modifié à base de diène conjugué, composition de caoutchouc modifiée le contenant, et procédé de préparation du polymère modifié à base de diène conjugué
KR20160071311A (ko) 변성 공역디엔계 중합체, 이를 포함하는 변성 고무 조성물 및 변성 공역디엔계 중합체의 제조방법
WO2020013638A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc comprenant celui-ci
WO2017150852A1 (fr) Modificateur à base d'azasilane et procédé de préparation d'un polymère à base de diène conjugué modifié à l'aide de celui-ci
WO2017078408A1 (fr) Composé d'organolithium, procédé de production d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié
WO2014175562A1 (fr) Procédé pour la production continue d'un polymère de diène conjugué modifié, polymère produit par le procédé, et composition de caoutchouc le comprenant
WO2017111487A1 (fr) Polymère à base d'un diène conjugué modifié et procédé de préparation de ce polymère
WO2018128290A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2016093496A1 (fr) Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation du polymère de diène conjugué modifié
WO2016017977A1 (fr) Polymère de diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de production de polymère diène conjugué modifié
WO2015056994A1 (fr) Polymère à base de diène conjugué fonctionnalisé en bout de chaîne et procédé pour le produire
WO2021085829A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2015057021A1 (fr) Polymère modifié à base d'un diène conjugué, son procédé de préparation et composition de caoutchouc en contenant
WO2016111445A1 (fr) Polymère diène conjugué modifié, composition de caoutchouc modifiée le comprenant, et procédé de préparation de polymère diène conjugué modifié
WO2016089035A1 (fr) Initiateur de polymérisation anionique comportant une extrémité terminale anionique comprenant un groupe amine, procédé de production d'un copolymère à base d'un diène conjugué modifié à l'aide de celui-ci et composition de caoutchouc comprenant ce copolymère à base d'un diène conjugué modifié ainsi produite

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15868082

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15121804

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016554594

Country of ref document: JP

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2015868082

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015868082

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE