WO2018097517A1 - Polymère à base de diène conjugué modifié et procédé de préparation de ce dernier - Google Patents

Polymère à base de diène conjugué modifié et procédé de préparation de ce dernier Download PDF

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Publication number
WO2018097517A1
WO2018097517A1 PCT/KR2017/012623 KR2017012623W WO2018097517A1 WO 2018097517 A1 WO2018097517 A1 WO 2018097517A1 KR 2017012623 W KR2017012623 W KR 2017012623W WO 2018097517 A1 WO2018097517 A1 WO 2018097517A1
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carbon atoms
formula
group
conjugated diene
hydrocarbon group
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PCT/KR2017/012623
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English (en)
Korean (ko)
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이형우
김노마
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주식회사 엘지화학
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Priority claimed from KR1020170146778A external-priority patent/KR102072088B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2018560821A priority Critical patent/JP6667015B2/ja
Priority to CN201780005836.2A priority patent/CN108473620B/zh
Priority to EP17874849.7A priority patent/EP3372622B1/fr
Priority to US16/062,927 priority patent/US11066487B2/en
Publication of WO2018097517A1 publication Critical patent/WO2018097517A1/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
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • 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
    • 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
    • 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
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • B60C1/0041—Compositions of the carcass layers
    • 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
    • C08C19/30—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
    • B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
    • 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
    • B60C2001/0066—Compositions of the belt layers

Definitions

  • the present invention relates to a modified conjugated diene-based polymer, and more particularly, to a modified conjugated diene-based polymer having excellent workability and excellent tensile strength, abrasion resistance, and wet road resistance by including a functional group derived from an inorganic filler and a modifying agent having excellent affinity. It relates to a polymer.
  • a method of reducing the hysteresis loss of the vulcanized rubber In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber.
  • As an evaluation index of the vulcanized rubber a repulsive elasticity of 50 ° C. to 80 ° C., tan ⁇ , Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature or a small tan ⁇ Goodrich heat generation is preferable.
  • the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and can reduce the movement of the chain end by the binding or modification of the chain end and increase the bonding strength with the filler such as silica or carbon black. It is used a lot as a rubber material.
  • solution polymerization SBR When such a solution polymerization SBR is used as a rubber material for tires, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to not only control tire demand properties such as running resistance and braking force, but also increase the glass transition temperature. Proper adjustment can reduce fuel consumption.
  • the solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers. For example, US Pat. No.
  • 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.
  • carbon black and silica are used as reinforcing fillers for tire treads, and when silica is used as reinforcing fillers, low hysteresis loss and wet road resistance are improved.
  • the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler may be used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent.
  • a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal portion but the effect is not sufficient.
  • the present invention has been made in order to solve the problems of the prior art, by including a functional group derived from an inorganic filler and a modifier excellent in affinity with sulfur and nitrogen atoms in the molecule at the same time, excellent processability, even with a high molecular weight,
  • An object of the present invention is to provide a modified conjugated diene-based polymer having excellent tensile strength, abrasion resistance, and wet road resistance, and a manufacturing method thereof.
  • the present invention includes a modified unit derived from a conjugated diene-based monomer, and includes a denaturation-derived functional group comprising a compound represented by the following formula (1) at one end Conjugated diene-based polymers are provided:
  • Z 1 and Z 2 are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or a substituent represented by the following Chemical Formula 2, but at least one of Z 1 and Z 2 is represented by the following Chemical Formula 2 It may be a substituent to be displayed,
  • X 1 may be S or N atom
  • n may be 1 when X 1 is S atom
  • n may be 2 when X 1 is N atom
  • a 1 may have 1 to 4 carbon atoms.
  • 30 may be a divalent hydrocarbon group
  • R 1 to R 3 are each independently halogen, a monovalent hydrocarbon group of 1 to 30 carbon atoms, or an alkoxy group of 1 to 30 carbon atoms, at least one of R 1 to R 3 It may be a halogen group or an alkoxy group having 1 to 30 carbon atoms.
  • the present invention comprises the step of polymerizing a conjugated diene-based monomer, or an aromatic vinyl monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organometallic compound (S1); And it provides a modified conjugated diene-based polymer manufacturing method comprising the step (S2) of reacting with a modifier comprising the active polymer and a compound represented by the formula (1):
  • the present invention provides a denaturing agent comprising the compound represented by Formula 1 and a preparation method thereof.
  • the conjugated diene-based polymer when the conjugated diene-based polymer is modified from a modifier having both sulfur and nitrogen atoms in a molecule and excellent in affinity with the inorganic filler, the functional group derived from the modifier is included at one end of the polymer, thereby It is possible to prepare a modified conjugated diene-based polymer excellent in chemical conversion, and the modified conjugated diene-based polymer thus prepared is excellent in processability, and has excellent tensile strength, wear resistance, and wet road resistance, even though it has a high molecular weight.
  • the modified conjugated diene-based polymer according to the present invention includes a repeating unit derived from a conjugated diene-based monomer, and may include a modifier-derived functional group including a compound represented by the following Chemical Formula 1 at one end thereof:
  • Z 1 and Z 2 are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or a substituent represented by the following Chemical Formula 2, but at least one of Z 1 and Z 2 is represented by the following Chemical Formula 2 It may be a substituent to be displayed,
  • X 1 may be S or N atom
  • n may be 1 when X 1 is S atom
  • n may be 2 when X 1 is N atom
  • a 1 may have 1 to 4 carbon atoms.
  • 30 may be a divalent hydrocarbon group
  • R 1 to R 3 are each independently halogen, a monovalent hydrocarbon group of 1 to 30 carbon atoms, or an alkoxy group of 1 to 30 carbon atoms, at least one of R 1 to R 3 It may be a halogen group or an alkoxy group having 1 to 30 carbon atoms.
  • Z 1 and Z 2 may each independently represent a hydrogen or a substituent represented by Formula 2, and at least one of Z 1 and Z 2 may be a substituent represented by Formula 2,
  • X 1 may be S or N atom
  • n may be 1 when X 1 is S atom
  • n may be 2 when X 1 is N atom
  • a 1 may have 1 to 4 carbon atoms.
  • R 1 to R 3 are each independently a halogen, a monovalent hydrocarbon group of 1 to 10 carbon atoms, or an alkoxy group of 1 to 10 carbon atoms, at least one of R 1 to R 3 It may be a halogen group or an alkoxy group having 1 to 10 carbon atoms.
  • the term 'monovalent hydrocarbon group' refers to a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group and an aryl group including one or more unsaturated bonds. Can be.
  • the term 'bivalent hydrocarbon group' is a two-membered carbon and hydrogen, such as a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including one or more unsaturated bonds, and an arylene group. It may mean a valence atom.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1-1 to 1-4.
  • Et is an ethyl group.
  • the conjugated diene-based polymer when the conjugated diene-based polymer is modified from a modifying agent having excellent affinity with an inorganic filler, including the compound represented by Formula 1 having both sulfur and nitrogen atoms in a molecule, at one end of the polymer
  • a modifying agent having excellent affinity with an inorganic filler including the compound represented by Formula 1 having both sulfur and nitrogen atoms in a molecule
  • the functional group derived from the modifier it is possible to prepare a modified conjugated diene-based polymer having excellent affinity with the inorganic filler, and the modified conjugated diene-based polymer thus prepared is excellent in processability even though having a high molecular weight, tensile strength, wear resistance And wet road surface resistance is excellent effect.
  • the conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed when the conjugated diene-based monomer is polymerized, and the conjugated diene-based monomer may be, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene , Piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom) It may be one or more.
  • the modified conjugated diene-based copolymer may be, for example, a copolymer further comprising an aromatic vinyl monomer-derived repeating unit together with the repeating unit derived from the conjugated diene-based monomer.
  • the aromatic vinyl monomer-derived repeating unit may mean a repeating unit formed by polymerization of an aromatic vinyl monomer, and the aromatic vinyl monomer may be, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, or 4-propyl. Styrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1-vinyl-5-hexylnaphthalene.
  • the modified conjugated diene-based polymer when the modified conjugated diene-based polymer is a copolymer including an aromatic vinyl monomer-derived repeating unit, the modified conjugated diene-based polymer may contain 50 to 95% by weight, 55 to 90% by weight, or 60 to 60% of the repeating unit derived from a conjugated diene monomer.
  • 90 wt% may include 5 to 50 wt%, 10 to 45 wt%, or 10 to 40 wt% of an aromatic vinyl monomer-derived repeating unit, and has excellent rolling resistance, wet road resistance, and abrasion resistance within this range. It works.
  • the modified conjugated diene-based copolymer may be a copolymer further comprising a modified monomer-derived repeating unit including a compound represented by the following formula 3 together with the repeating unit derived from the conjugated diene-based monomer, for example.
  • R 4 , R 5 and R 6 may be each independently hydrogen, a monovalent hydrocarbon group of 1 to 20 carbon atoms, R 7 is a single bond, a divalent hydrocarbon group of 1 to 20 carbon atoms, or NR 10 , O and S may be a hetero alkylene group containing one or more hetero atoms selected from the group consisting of, R 8 and R 9 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, or 1 to 30 carbon atoms Is a silyl group substituted with 1, 2 or 3 substituted hydrocarbon groups, or R 8 and R 9 may be bonded to each other to form a saturated or unsaturated cyclic structure having 3 to 20 carbon atoms with adjacent N atoms, and R 8 and R When 9 forms a cyclic structure, it may contain one or more heteroatoms selected from the group consisting of NR 11 , O and S, and R 10 and R 11 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, Or 1 to
  • the compound represented by Formula 3 may be N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-dibutylvinylbenzylamine, N, N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethylaminoethylstyrene, 2-bis (trimethylsilyl) aminoethylstyrene, 1- (4-N, N-dimethylaminophenyl)- 1-phenylethylene, N, N-dimethyl-2- (4-vinylbenzyloxy) ethylamine, N, N, N'-trimethyl-N '-(4-vinylbenzyl) ethane-1,2-diamine, N , N-dimethyl-2-((4-vinylbenzyl)
  • the modified monomer-derived repeating unit including the compound represented by Chemical Formula 3 may be, for example, included in the terminal portion of the polymer for replacing the functional group derived from the denaturant including the compound represented by Chemical Formula 1, and in this case, conjugated
  • the end portion of the diene-based polymer is end-capping to the repeating unit derived from the modified monomer, thereby having excellent affinity with the filler and excellent binding efficiency during the modification reaction or the coupling reaction with the modifier.
  • the copolymer may be a random copolymer, in this case there is an excellent balance between the physical properties.
  • the random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 5,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,500,000 g / mol, 50,000 g / mol to 1,000,000 g / mol, or from 100,000 g / mol to 500,000 g / mol, with a weight average molecular weight (Mw) of 10,000 g / mol to 10,000,000 g / mol, 50,000 g / mol to 5,000,000 g / mol, 100,000 g / mol to 3,000,000 g / mol, or 200,000 g / mol to 2,000,000 g / mol, there is an effect excellent in rolling resistance and wet road resistance within this range.
  • the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1 to 5, 1.2 to 4, or 1.2 to 3, and has an
  • the modified conjugated diene-based polymer may have a Mooney viscosity of 100 to 30, 120, 40 to 100, or 50 to 80, and has excellent workability and productivity within this range. .
  • the modified conjugated diene-based polymer may have a vinyl content of at least 5% by weight, 10% by weight to 70% by weight, or 20% by weight to 50% by weight, and within this range, the glass transition temperature may be adjusted to an appropriate range. It has the effect of excellent rolling resistance, wet road resistance and low fuel consumption.
  • the vinyl content may refer to the content of 1,2-added conjugated diene-based monomers, not 1,4-addition, based on 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer. Can be.
  • the terms 'derived repeating unit' and 'derived functional group' may refer to a component, a structure, or the substance itself derived from a substance.
  • the modified conjugated diene-based polymer manufacturing method is to prepare an active polymer in which an organic metal is bonded by polymerizing a conjugated diene-based monomer, or an aromatic vinyl monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organometallic compound. Step S1; And reacting with a denaturing agent including the active polymer and a compound represented by Formula 1 below (S2).
  • the hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
  • the compound represented by Chemical Formula 1 may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomers.
  • the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol, based on 100 g of the total monomer.
  • the organometallic compound is, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph Tilithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexylithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , Lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.
  • the polymerization of the step (S1) may be carried out including a modified monomer including a compound represented by the following formula (3).
  • the modified monomer including the compound represented by Formula 3 may be added simultaneously with, for example, the conjugated diene monomer, or the aromatic vinyl monomer and the conjugated diene monomer, and the conjugated diene monomer or the aromatic vinyl. After the addition of the monomer and the conjugated diene monomer may be added separately.
  • the modified monomer containing the compound represented by Formula 3 is added separately after the addition of the conjugated diene monomer, or the aromatic vinyl monomer and the conjugated diene monomer, end-capping the end of the active polymer (end-capping) has the effect.
  • the polymerization of the step (S1) may be carried out including a polar additive
  • the polar additive may be added 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g based on a total of 100g monomer. have.
  • the polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxy ethoxyethane , Bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine, and may be one or more selected from the group consisting of triethylamine.
  • It may be an amine or tetramethylethylenediamine, and may be the same as or different from the polar additives that may be added in the preparation of the amino silane-based compound, when the polar additives include conjugated diene monomer, or conjugated diene monomer and When copolymerizing aromatic vinyl monomers, the difference in reaction rate It has an effect of inducing to easily form a random copolymer by giving.
  • the polymerization of the step (S1) may be, for example, anionic polymerization, and specifically, may be living anion polymerization having an anion active site at the end of the polymerization by a growth polymerization reaction by anion.
  • the polymerization of the step (S1) may be a temperature increase polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization)
  • the constant temperature polymerization may include the step of polymerization by the heat of reaction without the addition of heat after the addition of the organometallic compound optionally
  • the temperature polymerization may mean a polymerization method in which the temperature is increased by optionally adding heat after the organometallic compound is added, and the isothermal polymerization is heat after adding the organometallic compound.
  • the polymerization of the step (S1) may be carried out in a temperature range of -20 °C to 200 °C, 0 °C to 150 °C, or 10 °C to 120 °C as an example.
  • the active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organic metal cation are combined.
  • the molar ratio of the denaturant and the organometallic compound including the compound represented by Chemical Formula 1 may be 1: 0.1 to 1:10, and the modification performance of the optimum performance may be performed within this range. It is possible to obtain a conjugated diene polymer of high modification rate.
  • the reaction of step (S2) is a modification reaction for introducing a functional group derived from the modifier into the active polymer, it may be to perform the reaction for 1 minute to 5 hours at 0 °C to 90 °C.
  • the modified conjugated diene-based polymer manufacturing method may be performed by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.
  • the modified conjugated diene-based polymer manufacturing method may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary, following the step (S2) of the present invention.
  • the denaturing agent according to the present invention may include a compound represented by Formula 1 below:
  • the denaturant of the present invention has both sulfur and nitrogen atoms in the molecule at the same time, and has excellent affinity with inorganic fillers, particularly silica fillers, thereby increasing the dispersibility between the polymer modified from the modifier and the filler.
  • the denaturant including the compound represented by Chemical Formula 1 may be prepared by reacting the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 (S3):
  • Y 1 and Y 2 are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, SH, or NH 2 , but at least one of Y 1 and Y 2 may be SH or NH 2.
  • Q may be a halogen group
  • a 1 may be a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 1 to R 3 are each independently a halogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or carbon atoms
  • An alkoxy group of 1 to 30, but at least one of R 1 to R 3 may be a halogen group or an alkoxy group of 1 to 30 carbon atoms.
  • a rubber composition comprising the modified conjugated diene-based polymer.
  • the rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, tensile strength, wear resistance, and the like. It is excellent in the mechanical properties of and excellent in the balance between each physical property.
  • the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition.
  • the other rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
  • the rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene),
  • the rubber composition may include, for example, 0.1 part by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention.
  • the filler may be, for example, a silica-based filler, and specific examples may be wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate, colloidal silica, and the like.
  • the wet silica may be the most compatible of the grip (wet grip).
  • the rubber composition may further include a carbon black filler as needed.
  • silica when silica is used as the filler, a silane coupling agent for improving reinforcement and low heat generation may be used together.
  • the silane coupling agent may include bis (3-triethoxysilylpropyl) tetrasulfide.
  • the compounding amount of the silane coupling agent is conventional.
  • the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of silica, and the effect as a coupling agent is within this range. While sufficiently exhibiting, there is an effect of preventing gelation of the rubber component.
  • the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent.
  • the vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the rubber component, while ensuring the required elastic modulus and strength of the vulcanized rubber composition within this range and at the same time low fuel efficiency. Excellent effect.
  • the rubber composition according to an embodiment of the present invention in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white, Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
  • the vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG.
  • a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG.
  • Guanidine-based compounds such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
  • the process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering the tensile strength and abrasion resistance, when the aromatic process oil, hysteresis loss and low temperature characteristics are considered.
  • Naphthenic or paraffinic process oils may be used.
  • the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.
  • the anti-aging agent is for example N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone, and the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.
  • the rubber composition according to an embodiment of the present invention may be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the compounding formulation, and has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.
  • a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc.
  • the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.
  • the present invention provides a tire including the rubber composition.
  • the tire may be manufactured using the rubber composition.
  • the tire may include a tire or a tire tread.
  • Example 1 Except that 1.63 g (4 mmol) of the compound represented by the following formula 1-2 was added instead of the compound represented by the formula 1-1, it was carried out in the same manner as in Example 1.
  • Example 1 Except that 1.34 g (4 mmol) of the compound represented by the following formula 1-3 was added instead of the compound represented by the formula 1-1, it was carried out in the same manner as in Example 1.
  • Example 1 0.835 g (4 mmol) of tetraethoxysilane (TESO) was added instead of the compound represented by Chemical Formula 1-1, and the same method as in Example 1 was performed.
  • TSO tetraethoxysilane
  • Example 1 In Example 1, except that 1.12 g (4 mmol) of N, N-diethylaminopropyltriethoxysilane was added instead of the compound represented by Formula 1-1. It carried out by the same method as Example 1.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatohraph (GPC) analysis, and the molecular weight distribution (MWD, Mw / Mn) was calculated from the respective measured molecular weights.
  • GPC gel permeation chromatohraph
  • Mw molecular weight distribution
  • the GPC used a combination of two PLgel Olexis (Polymer Laboratories Co.) column and one PLgel mixed-C (Polymer Laboratories Co.) column, all of the newly replaced column was a mixed bed column,
  • the GPC standard material was calculated using polystyrene (PS) when calculating the molecular weight.
  • the pattern viscosity (MV, (ML1 + 4, @ 100 °C) MU) was measured using a Rotor Speed 2 ⁇ 0.02 rpm, Large Rotorfmf at 100 °C using MV-2000 (ALPHA Technologies, Inc.), the sample used After leaving at room temperature (23 ⁇ 3 °C) for 30 minutes or more, 27 ⁇ 3 g was collected and filled into the die cavity, and the platen was operated for 4 minutes.
  • the modified modified conjugated diene-based polymers of Examples and Comparative Examples were blended under the blending conditions shown in Table 2 below as raw rubber.
  • the raw materials in Table 2 are each parts by weight based on 100 parts by weight of rubber.
  • the rubber specimen is kneaded through the first stage kneading and the second stage kneading.
  • the raw rubber modified conjugated diene-based polymer
  • filler modified conjugated diene-based polymer
  • organosilane coupling agent process oil
  • zincation zincation
  • stearic acid antioxidant
  • anti-aging agent anti-aging agent
  • wax wax
  • a half-variety mixer equipped with a temperature controller. Kneaded.
  • the temperature of the kneader was controlled to obtain a primary blend at a discharge temperature of 140 ° C to 150 ° C.
  • the primary compound, rubber promoter, sulfur, and a vulcanization accelerator were added to the kneader, and it mixed at the temperature of 60 degrees C or less, and obtained the secondary compound. Thereafter, rubber specimens were prepared through a curing process at a time multiplied by 1.3 times t90 at 160 ° C.
  • Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.
  • the load was measured at 6 pounds and 1000 revolutions and indexed. The smaller the index value, the better the wear resistance.
  • Viscoelastic properties were measured by using a dynamic mechanical analyzer (TA Co., Ltd.) to determine the tan ⁇ by varying the strain at a frequency of 10 Hz and each measurement temperature (-60 ° C. to 60 ° C.) in a torsion mode.
  • the modified conjugated diene-based polymers of Examples 1 to 3 according to the present invention have tensile properties, wear resistance and viscoelastic properties compared to the unmodified or modified conjugated diene-based polymers of Comparative Examples 1 to 3. All this was confirmed to be an improvement in seo.
  • the modified conjugated diene-based polymers of Examples 1 to 3 exhibit equivalent levels of wear resistance compared to the unmodified conjugated diene-based polymer of Comparative Example 1, with 300% modulus, tensile strength, tan ⁇ at 60 ° C. and 60 ° C. All tan ⁇ at showed a markedly elevated effect.
  • the modified conjugated diene-based polymers of Examples 1 to 3 were abrasion resistant and 300% modulus, compared to Comparative Examples 2 and 3, which were modified but prepared using an ethoxysilane or a modifying agent having only an ethoxysilane and an amine group.
  • Tensile strength, tan ⁇ at 0 ° C. and tan ⁇ at 60 ° C. were all significantly increased.
  • the conjugated diene-based polymer is modified from a modifier having both sulfur and nitrogen atoms in a molecule and excellent inorganic affinity with an inorganic filler according to the present invention
  • the inorganic filler is included at one end of the polymer by including a functional group derived from the modifier. Excellent affinity with, it was confirmed that all excellent tensile properties, wear resistance and viscoelastic properties.

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

Abstract

La présente invention concerne un polymère à base de diène conjugué modifié. Plus spécifiquement, l'invention concerne un polymère à base de diène conjugué modifié et son procédé de production, le polymère à base de diène conjugué modifié comprenant une unité de répétition dérivée d'un monomère à base de diène conjugué, et comprenant, au niveau d'une terminaison, un groupe fonctionnel dérivé d'un dénaturant comprenant un composé représenté par la formule chimique 1
PCT/KR2017/012623 2016-11-28 2017-11-08 Polymère à base de diène conjugué modifié et procédé de préparation de ce dernier WO2018097517A1 (fr)

Priority Applications (4)

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JP2018560821A JP6667015B2 (ja) 2016-11-28 2017-11-08 変性共役ジエン系重合体及びその製造方法
CN201780005836.2A CN108473620B (zh) 2016-11-28 2017-11-08 改性共轭二烯类聚合物及其制备方法
EP17874849.7A EP3372622B1 (fr) 2016-11-28 2017-11-08 Polymère modifié à base de diène conjugué et son procédé de préparation
US16/062,927 US11066487B2 (en) 2016-11-28 2017-11-08 Modified conjugated diene-based polymer and method of preparing the same

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CN113956411A (zh) * 2020-07-20 2022-01-21 中国石油天然气股份有限公司 共轭二烯烃的调节剂及其应用

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US4397994A (en) 1980-09-20 1983-08-09 Japan Synthetic Rubber Co., Ltd. High vinyl polybutadiene or styrene-butadiene copolymer
WO2004020475A1 (fr) * 2002-08-30 2004-03-11 Bridgestone Corporation Polymeres fonctionnalises et vulcanisats ameliores obtenus a partir de ceux-ci
WO2013031599A1 (fr) * 2011-08-26 2013-03-07 旭化成ケミカルズ株式会社 Procédé de production d'un polymère de diène conjugué dénaturé, polymère de diène conjugué dénaturé, composition le contenant, composition de caoutchouc, et pneu
KR20130044533A (ko) * 2011-10-24 2013-05-03 경상대학교산학협력단 신규한 실란 커플링제, 이의 제조방법 및 이를 포함하는 유기 탄성체
KR20150134035A (ko) * 2014-05-21 2015-12-01 주식회사 엘지화학 변성 공역디엔계 중합체의 제조방법
KR20160029029A (ko) * 2013-07-02 2016-03-14 시코쿠가세이고교가부시키가이샤 아졸실란 화합물, 표면 처리액, 표면 처리 방법 및 그 이용

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397994A (en) 1980-09-20 1983-08-09 Japan Synthetic Rubber Co., Ltd. High vinyl polybutadiene or styrene-butadiene copolymer
WO2004020475A1 (fr) * 2002-08-30 2004-03-11 Bridgestone Corporation Polymeres fonctionnalises et vulcanisats ameliores obtenus a partir de ceux-ci
WO2013031599A1 (fr) * 2011-08-26 2013-03-07 旭化成ケミカルズ株式会社 Procédé de production d'un polymère de diène conjugué dénaturé, polymère de diène conjugué dénaturé, composition le contenant, composition de caoutchouc, et pneu
KR20130044533A (ko) * 2011-10-24 2013-05-03 경상대학교산학협력단 신규한 실란 커플링제, 이의 제조방법 및 이를 포함하는 유기 탄성체
KR20160029029A (ko) * 2013-07-02 2016-03-14 시코쿠가세이고교가부시키가이샤 아졸실란 화합물, 표면 처리액, 표면 처리 방법 및 그 이용
KR20150134035A (ko) * 2014-05-21 2015-12-01 주식회사 엘지화학 변성 공역디엔계 중합체의 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956411A (zh) * 2020-07-20 2022-01-21 中国石油天然气股份有限公司 共轭二烯烃的调节剂及其应用
CN113956411B (zh) * 2020-07-20 2024-03-01 中国石油天然气股份有限公司 共轭二烯烃的调节剂及其应用

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