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WO2017188641A2 - Polymère à base de diène conjugué modifié et procédé de préparation associé - Google Patents

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

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Publication number
WO2017188641A2
WO2017188641A2 PCT/KR2017/004114 KR2017004114W WO2017188641A2 WO 2017188641 A2 WO2017188641 A2 WO 2017188641A2 KR 2017004114 W KR2017004114 W KR 2017004114W WO 2017188641 A2 WO2017188641 A2 WO 2017188641A2
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Prior art keywords
carbon atoms
group
conjugated diene
formula
substituted
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PCT/KR2017/004114
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English (en)
Korean (ko)
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WO2017188641A3 (fr
Inventor
손해성
김노마
김진영
서경창
이상미
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020170048685A external-priority patent/KR102014521B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/761,320 priority Critical patent/US10533062B2/en
Priority to EP17789826.9A priority patent/EP3333199B1/fr
Priority to CN201780003390.XA priority patent/CN108350118B/zh
Priority to JP2018522735A priority patent/JP6651621B2/ja
Priority to CN202010514552.XA priority patent/CN111763274B/zh
Publication of WO2017188641A2 publication Critical patent/WO2017188641A2/fr
Publication of WO2017188641A3 publication Critical patent/WO2017188641A3/fr

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  • the present invention relates to a modified conjugated diene-based polymer, a preparation method thereof and a rubber composition comprising the same.
  • the evaluation index of the vulcanized rubber is used as a repulsive elasticity of 50 ° C. to 80 ° C., tan ⁇ and Goodrich heat generation. . That is, a rubber material having a high rebound elasticity at the above temperature or a small tan ⁇ or good rich heat generation is preferable.
  • conjugated diene-based (co) polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. .
  • SBR styrene-butadiene rubber
  • BR butadiene rubber
  • 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 controlled by coupling or modification. Can be. Therefore, it is easy to change the structure of the final manufactured SBR or BR rubber, and can reduce the movement of the chain end by the binding or modification of the chain end and increase the bonding force with the filler such as silica or carbon black. It is used a lot as a rubber material.
  • the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby controlling tire required properties such as running resistance and braking force, and properly adjusting the glass transition temperature. By adjusting the fuel consumption can be reduced.
  • 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.
  • an anionic polymerization initiator 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, a monofunctional initiator, 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, hysteresis loss is small and wet skid resistance is improved.
  • the hydrophilic surface silica has a disadvantage of poor dispersibility due to its low affinity with conjugated diene rubber compared to the hydrophobic surface carbon black, so that it is necessary to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a silane coupling agent.
  • silica dispersibility in the rubber composition is improved, and the bond with the silica particles reduces the mobility of the end of the rubber molecule, thereby reducing the hysteresis loss. Attempts have been made to reduce, but the effect is insufficient.
  • the present invention has been made to solve the problems of the prior art, and includes a modified styrene-based compound-derived functional group and an aminosilane-based compound-based functional group modified modified conjugated diene system showing excellent affinity for the filler in the rubber composition It is to provide a polymer.
  • Another object of the present invention is to provide a method for preparing the modified conjugated diene polymer using a substituted styrene compound and an aminosilane compound.
  • Another object of the present invention to provide a rubber composition comprising the modified conjugated diene-based polymer.
  • a modified conjugated diene-based polymer comprising an aminosilane-based compound of formula 1 and a substituted styrene-based compound of formula (2):
  • a 1 and A 2 are each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms,
  • R 1 to R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
  • L 1 to L 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
  • R 5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms
  • D is a monovalent hydrocarbon group having 1 to 5 carbon atoms containing N or O,
  • k is an integer of 0-5.
  • a step of preparing a modified initiator composition by reacting the substituted styrene-based compound of Formula 2 with the organic alkali metal compound (step 1); Preparing an active polymer by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of the modification initiator composition (step 2); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (step 3) of reacting the active polymer and the aminosilane-based compound of formula (1).
  • a 1 and A 2 are each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms,
  • R 1 to R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
  • L 1 to L 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
  • R 5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms
  • D is a monovalent hydrocarbon group having 1 to 5 carbon atoms containing N or O,
  • k is an integer of 0-5.
  • a rubber composition comprising the modified conjugated diene-based polymer.
  • the modified conjugated diene-based polymer according to the present invention may exhibit a high modification rate by including a functional group derived from an aminosilane-based compound of Formula 1 and a functional group derived from a substituted styrene-based compound of Formula 2 at both ends of the main chain, and in particular, By including a tertiary amino group derived from the aminosilane-based compound of Formula 1, it can exhibit excellent affinity for the filler when applied to the rubber composition, as a result prevents agglomeration of the filler in the rubber composition and improves the dispersibility of the filler to increase the rubber composition Can improve the workability.
  • the method for producing a modified conjugated diene-based polymer according to the present invention to obtain a modified initiator composition by reacting the substituted styrene-based compound and the organometallic compound of the formula (2) before the polymerization reaction, by performing a polymerization reaction using this at one end
  • the active polymer to which the substituted styrene-based compound-derived functional group is introduced can be formed, and then, by reacting with the aminosilane-based compound of Formula 1, the aminosilane-based compound-derived functional group is bonded to the other end thereof, resulting in both ends of the main chain.
  • a modified conjugated diene-based polymer having a high modification rate into which a functional group is introduced can be prepared.
  • the rubber composition according to the present invention can improve the physical properties of the molded article produced by including the modified conjugated diene-based polymer, in particular, it is possible to improve the fuel efficiency, wear characteristics and braking characteristics of the tire with good balance.
  • the modified conjugated diene-based polymer according to the present invention a method for producing the same, and a rubber composition including the same can be easily applied to an industry requiring a modified conjugated diene-based polymer, such as a tire industry.
  • the term "monovalent hydrocarbon group” used in the present invention refers to a monovalent substituent derived from a hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group and an aryl group including one or more unsaturated bonds, and the like. May represent a monovalent atomic group in which carbon and hydrogen are bonded, and the monovalent atomic group may have a linear or branched structure according to the structure of the bond.
  • divalent hydrocarbon group used in the present invention refers to a divalent substituent derived from a hydrocarbon group, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkyl including at least one unsaturated bond.
  • a divalent atomic group in which carbon and hydrogen, such as a ethylene group and an arylene group, are bonded may be represented, and the divalent atomic group may have a linear or branched structure according to the structure of the bond.
  • the present invention provides a modified conjugated diene-based polymer having high affinity with filler and capable of expressing excellent processability.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that it comprises a functional group derived from the aminosilane-based compound of formula 1 and a substituted styrene-based compound derived from the formula (2).
  • a 1 and A 2 are each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms,
  • R 1 to R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
  • L 1 to L 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
  • R 5 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms
  • D is a monovalent hydrocarbon group having 1 to 5 carbon atoms containing N or O,
  • k is an integer of 0-5.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared through the production method described below, the functional group derived from the substituted styrene-based compound of Formula 2 is bonded to one end of the main chain, The functional group derived from the aminosilane-based compound of 1 may be bonded to the other terminal. That is, the modified conjugated diene-based polymer according to the present invention may include a functional group at both ends, thereby exhibiting a high modification rate and greatly improving physical properties.
  • the alkoxysilane structure is bonded to the conjugated diene-based polymer activation terminal, while the Si-O-Si structure and two amino groups bonded to the terminal
  • the Si-O-Si structure and two amino groups bonded to the terminal By exhibiting an affinity for fillers such as silica, it is possible to promote bonding of the filler with the modified conjugated diene-based polymer as compared with the conventionally modified agent containing one amino group in the molecule.
  • the molecular weight can be easily adjusted as compared with the conventional denaturing agent having six alkoxy groups bonded to the Si-O-Si-O-Si group, Not only is the molecular weight distribution narrow, but also the degree of bonding of the active ends of the conjugated diene-based polymer is uniform, and upon observation of changes in the molecular weight distribution before and after coupling, the molecular weight distribution is constant without being larger than before even after coupling.
  • the amino silane-based compound of Formula 1 may include an amino group, that is, a tertiary amino group which is a functional group that can improve the dispersibility of the filler by preventing aggregation between the filler in the rubber composition.
  • an amino group that is, a tertiary amino group which is a functional group that can improve the dispersibility of the filler by preventing aggregation between the filler in the rubber composition.
  • silica when silica is used as a filler, aggregation is likely to occur due to hydrogen bonding between hydroxyl groups present on the surface.
  • the dispersibility of silica can be improved by tertiary amino groups in the said aminosilane type compound interrupting the hydrogen bond of hydroxyl groups.
  • the aminosilane-based compound exhibits excellent affinity for the solvent used for the modification reaction of the filler affinity functional group and the polymer that can improve the wear resistance and processability of the rubber composition by interacting with the filler with the amino group described above. It may include a solvent affinity functional group.
  • the filler affinity functional group is specifically an alkoxysilane group, which is introduced into the polymer and then condensed with a functional group on the filler surface, such as silanol on the silica surface when the filler is silica, to improve the wear resistance and processability of the polymer. Can be. This improvement can be improved as the number of alkoxysilane groups increases.
  • the solvent-affinity functional group may specifically increase the solubility of the aminosilane-based compound in the solvent during the modification reaction of the polymer as a hydrocarbon group such as an alkyl group, and as a result, may improve the modification rate of the polymer.
  • a 1 and A 2 may be independently selected from the group consisting of a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a combination thereof.
  • a 1 or A 2 is a combination group, specifically-[(X) m- (Y) n ]-(where X and Y are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or carbon number Arylene groups of 6 to 20, wherein X and Y are not identical to each other, and m and n are each independently integers of 1 to 3).
  • a 1 and A 2 may be each independently an alkylene group having 1 to 10 carbon atoms, and even more specifically, an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, or a propylene group.
  • an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, or a propylene group.
  • a 1 and A 2 may be each independently an alkylene group having 1 to 3 carbon atoms such as methylene group, ethylene group or propylene group, and Specifically, it may be a methylene group or an ethylene group, and more specifically, a methylene group.
  • a 1 and A 2 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, and an aryl having 6 to 12 carbon atoms.
  • R 1 to R 4 are each independently a substituted or unsubstituted cycloalkyl group having a carbon number of 1 to 20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, having 3 to 20 carbon atoms in the ,
  • L 1 to L 4 may be each independently a substituted or unsubstituted C1-20 monovalent hydrocarbon group, and in particular, a substituted or unsubstituted C1-20 alkyl group, C2-2 Selected from the group consisting of an alkenyl group of 20, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, and an alkylaryl group of 7 to 20 carbon atoms More specifically, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, alkylaryl group having 7 to 12 carbon atoms and 7 to 12 carbon atoms It may be selected from the group consisting of an arylalkyl group.
  • L 1 to L 4 is alkyl group having 1 to 6 carbon atoms each independently unsubstituted or substituted independently of each other.
  • the L 1 to L 4 may be substituted with substituents as described above in A 1 and A 2 .
  • a 1 and A 2 are each independently an alkylene group having 1 to 3 carbon atoms
  • R 1 to R 4 are each independently 1 to 6 carbon atoms. It may be an alkyl group
  • L 1 to L 4 may be each independently an alkyl group having 1 to 6 carbon atoms.
  • aminosilane-based compound of Formula 1 may be a compound of Formulas 1a to 1c, any one or a mixture of two may be used.
  • the aminosilane-based compound of Formula 1 having the above structure may be prepared directly using a known chemical reaction, or may be obtained commercially.
  • the substituted styrene-based compound of Formula 2 may include a filler affinity functional group that can improve the wear resistance and processability of the rubber composition by interaction with the filler.
  • R 5 may be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • D may include N or O instead of one or more carbon atoms in the hydrocarbon group, or one or more hydrogen atoms bonded to carbon atoms in the hydrocarbon group may be substituted with N or O.
  • D may be an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 5 carbon atoms including N or O.
  • k may be an integer of 0 to 5, and specifically, may be an integer of 2 to 3.
  • R 5 is a hydrogen atom in the formula (2)
  • D is an alkyl group having 1 to 3 carbon atoms containing N or O or a cycloalkyl group having 3 to 5 carbon atoms
  • k May be an integer from 2 to 3.
  • substituted styrene-based compound of Formula 2 may be a compound of Formula 2a.
  • the conjugated diene polymer may be a homopolymer of a conjugated diene monomer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
  • the copolymer is a random copolymer in which structural units constituting the copolymer are randomly arranged and bonded, including a structural unit derived from a conjugated diene monomer and a structural unit derived from an aromatic vinyl monomer. It may be.
  • the modified conjugated diene-based polymer may have a narrow molecular weight distribution (Mw / Mn) (or also referred to as polydispersity index (PDI)) of 1.1 to 3.0. If the molecular weight distribution of the modified conjugated diene-based polymer is more than 3.0, or less than 1.1, there is a fear that the tensile properties and viscoelasticity when applied to the rubber composition. Considering the remarkable effect of the tensile properties and viscoelasticity improving effect of the polymer according to the molecular weight distribution control, the molecular weight distribution of the modified conjugated diene-based polymer may be specifically 1.3 to 2.0. Moreover, the said modified conjugated diene type polymer is similar to the molecular weight distribution in the case of a conjugated diene type polymer before modification
  • Mw / Mn narrow molecular weight distribution
  • the molecular weight distribution of the modified butadiene-based polymer can be calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
  • the number average molecular weight (Mn) is a common average of individual polymer molecular weights obtained by measuring the molecular weight of n polymer molecules and calculating the sum of these molecular weights and dividing by n
  • the weight average molecular weight (Mw) is a polymer.
  • the molecular weight distribution of the composition is shown. All molecular weight averages can be expressed in grams per mole (g / mol).
  • the said weight average molecular weight and number average molecular weight are polystyrene conversion molecular weights analyzed by gel permeation chromatography (GPC), respectively.
  • the modified conjugated diene-based polymer may satisfy the above molecular weight distribution conditions and may have a number average molecular weight (Mn) of 50,000 g / mol to 2,000,000 g / mol, more specifically 200,000 g / mol to 800,000 g It may be / mol.
  • the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 100,000 g / mol to 4,000,000 g / mol, more specifically 300,000 g / mol to 1,500,000 g / mol.
  • the weight average molecular weight (Mw) of the modified conjugated diene-based polymer is less than 100,000 g / mol or the number average molecular weight (Mn) is less than 50,000 g / mol there is a fear of lowering the tensile properties when applied to the rubber composition.
  • the weight average molecular weight (Mw) exceeds 4,000,000 g / mol or the number average molecular weight (Mn) exceeds 2,000,000 g / mol
  • the workability of the rubber composition is deteriorated due to the decrease in processability of the modified conjugated diene-based polymer. Kneading becomes difficult, and it may be difficult to sufficiently improve the physical properties of the rubber composition.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention simultaneously meets the weight average molecular weight (Mw) and the number average molecular weight conditions together with the above molecular weight distribution, the rubber composition when applied to the rubber composition It is possible to improve the balance without biasing the tensile properties, viscoelasticity and workability.
  • the modified conjugated diene-based polymer has a vinyl group content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% by weight to 60% by weight, based on the total weight of the polymer.
  • the glass transition temperature can be adjusted to an appropriate range to improve the properties required for the tire, such as running resistance and braking force when applied to the tire.
  • the vinyl content is a repeating unit content of the structure derived from 1,2-added conjugated diene monomer instead of 1,4-addition based on the total weight of the conjugated diene polymer composed of a monomer having a vinyl group or a conjugated diene monomer. It is expressed as a percentage.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) of 40 to 140, specifically 60 to 100 at 100 °C. When it has the Mooney viscosity of the above-mentioned range, it can exhibit more excellent workability.
  • MV Mooney viscosity
  • the Mooney viscosity can be measured using a Mooney viscometer, for example, Rotor Speed 2 ⁇ 0.02rpm, Large Rotor at 100 ° C with MV2000E from Monsanto.
  • the sample used can be measured by leaving the plate at 27 ⁇ 3g after filling at the room temperature (23 ⁇ 3 °C) for more than 30 minutes and operating the platen.
  • a method for preparing the modified conjugated diene-based polymer using a modification initiator composition comprising the aminosilane-based compound of Formula 1 and substituted styrene-based compound of Formula 2.
  • the preparation method comprises the steps of preparing a modified initiator composition by reacting the substituted styrene-based compound of Formula 2 with the organic alkali metal compound in a hydrocarbon solvent (step 1); Preparing an active polymer by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of the modification initiator composition (step 2); And reacting the active polymer with the aminosilane-based compound of Formula 1 (Step 3).
  • Step 1 is a step for preparing a modified initiator composition, which may be performed by reacting the substituted styrene-based compound with an organic alkali metal compound in a hydrocarbon solvent, wherein the modified initiator composition is added to the substituted styrene-based compound oligomer. It may include a modification initiator compound having a structure in which an alkyl alkali metal derived from an organic alkali metal compound is introduced.
  • 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 organoalkali metal compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. Specifically, the organic alkali metal compound may be used in an amount of 0.05 mmol to 5 mmol, more specifically 0.1 mmol to 3 mmol, even more specifically 0.1 mmol to 2 mmol, based on 100 g of the monomer.
  • the organoalkali metal compound is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, Phenyllithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naph At least one member selected from the group consisting of sodium sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isoprop
  • the substituted styrene-based compound may be used in 0.1 mol to 3.0 mol relative to 1 mol of the organic alkali metal compound.
  • Step 2 is a step for preparing an active polymer combined with a functional group and an alkali metal derived from the substituted styrene-based compound, polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of the modification initiator composition. This can be done by.
  • the preparation method according to an embodiment of the present invention may form a polymer main chain by polymerizing a monomer using the modification initiator composition and simultaneously introduce the substituted styrene-based compound-derived functional group at one end. Therefore, the polymerization of step 2 may be a first modification step.
  • the polymerization of step 2 may be one using a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer together. That is, the polymer prepared by the above production method according to an embodiment of the present invention may be a conjugated diene monomer homopolymer or a copolymer derived from a conjugated diene monomer and an aromatic vinyl monomer.
  • the conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.
  • the conjugated diene monomer may include 60% by weight or more of the unit derived from the conjugated diene monomer in the finally prepared modified conjugated diene polymer. 60 wt% to 90 wt%, more specifically, 60 wt% to 85 wt%.
  • the aromatic vinyl monomer is not particularly limited, but for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p It may be one or more selected from the group consisting of -methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.
  • the aromatic vinyl monomer may be 40 wt% or less of the aromatic vinyl monomer-derived unit in the finally prepared modified conjugated diene polymer. It may be used in an amount comprised from 10% by weight to 40% by weight, more specifically 15% by weight to 40% by weight.
  • the reaction of step 1 and the polymerization of step 2 may each be performed by further adding a polar additive as needed, and the polar additive may be added in an amount of 0.001 part by weight to 1.0 part by weight based on 100 parts by weight of the total monomer. . Specifically, the amount may be added in an amount of 0.005 parts by weight to 0.5 parts by weight, and more specifically 0.01 parts by weight to 0.3 parts by weight based on 100 parts by weight of the total monomers.
  • the polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethyl Aminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.
  • the reaction rate can be easily compensated for by forming a random copolymer. Can be induced.
  • step 2 may be carried out through adiabatic polymerization, or isothermal polymerization.
  • adiabatic polymerization refers to a polymerization method including a step of polymerizing with self-heating reaction without adding heat after the addition of the organoalkali metal compound, and the isothermal polymerization is an arbitrary heat after adding the organoalkali metal compound. It represents a polymerization method for maintaining a constant temperature of the polymer by adding or taking away heat.
  • the polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically 0 ° C to 150 ° C, and more specifically 10 ° C to 120 ° C.
  • Step 3 is a modification step of reacting the active polymer with an aminosilane-based compound of Formula 1 to prepare a modified conjugated diene-based polymer.
  • the aminosilane-based compound of Formula 1 may be used in a ratio of 0.1 mol to 2.0 mol relative to 1 mol of the organic alkali metal compound.
  • the reaction of step 3 is a modification reaction for introducing functional groups into the polymer, each reaction may be performed for 1 minute to 5 hours at a temperature range of 0 °C to 90 °C.
  • the production method according to an embodiment of the present invention may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary after step 3 above.
  • a rubber composition comprising the modified conjugated diene-based polymer.
  • the rubber composition may improve the physical properties of the molded article by including the modified conjugated diene-based polymer, and in particular, it is possible to improve the fuel efficiency, wear characteristics and braking characteristics of the tire with good balance.
  • the rubber composition may include a modified conjugated diene-based polymer in an amount of 0.1 wt% or more and 100 wt% or less, specifically 10 wt% to 100 wt%, and more specifically 20 wt% to 90 wt%. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, improvement effects on fuel efficiency, wear characteristics, and braking characteristics in a molded article manufactured using the rubber composition, such as a tire, may be insignificant.
  • 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 modified conjugated diene copolymer may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight.
  • the rubber component may be natural rubber or synthetic rubber, for example, the rubber component may 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 0.1 part by weight to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.
  • the filler may be a silica-based filler or a carbon black-based filler, and any one or a mixture thereof may be used.
  • the filler may be silica, and more specifically, it may be wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate or colloidal silica. More specifically, the filler may be a wet silica having the most remarkable effect of improving the breaking characteristics and wet grip (wet grip).
  • a silane coupling agent may be used together to improve reinforcement and low heat generation.
  • silane coupling agent examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N
  • the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.
  • a modified conjugated diene-based polymer having a functional group having a high affinity with a silica-based filler in an active site is used as a rubber component.
  • the compounding amount can be reduced than usual.
  • the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the silica-based filler. When used in the above range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.
  • the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus 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 based on 100 parts by weight of the rubber component. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.
  • 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, in particular, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
  • the vulcanization accelerator is not particularly limited, and specifically M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used.
  • the vulcanization accelerator may be included in an amount of 0.1 parts by weight 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, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties.
  • the process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel consumption) of the vulcanized rubber.
  • the anti-aging agent specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone.
  • the anti-aging agent may be used in an amount of 0.1 parts by weight 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 can be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also 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 tires such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, or bead coated rubbers, and various industrial applications such as dustproof rubbers, belt conveyors, and hoses. It may be useful in the manufacture of rubber products.
  • SM Styrene derived units
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each copolymer were measured by gel permeation chromatography (GPC) analysis under the conditions of 40 ° C.
  • the column (column) was used in combination with two bags of PLgel Olexis of Polymer Laboratories Co., Ltd. and one PLgel mixed-C column, all of the newly replaced column was a mixed bed column.
  • PS polystyrene
  • the polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by the above method.
  • the Mooney viscosity of each copolymer was measured by MV-2000 (Alpha Technologies Co., Ltd.) for 15 minutes or more of each sample weight 15g or more for 1 minute and then at 100 °C for 4 minutes.
  • Each rubber composition was prepared through a first stage kneading, a second stage kneading and a third stage kneading.
  • the amount of the material excluding the copolymer is shown based on 100 parts by weight of the copolymer.
  • 100 parts by weight of each copolymer, 70 parts by weight of silica, and bis (3-triethoxysilylpropyl) tetrasulfate as a silane coupling agent were used at 80 rpm using a half-barrier with temperature controller.
  • the second stage kneading after cooling the primary blend to room temperature, 1.75 parts by weight of a rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2.0 parts by weight of vulcanization accelerator are added to the kneader, and the mixture is mixed at a temperature of 60 ° C. or lower to mix the secondary mixture. Got. Thereafter, the second compound was molded in a third stage kneading, and vulcanized by vulcanization press at 180 ° C. for t90 + 10 minutes to prepare each vulcanized rubber.
  • CZ rubber accelerator
  • sulfur powder 1.5 parts by weight of sulfur powder
  • vulcanization accelerator 2.0 parts by weight of vulcanization accelerator
  • Tensile properties were prepared in accordance with the tensile test method of ASTM 412 (thickness 25 mm, length 80 mm) and measured the tensile strength at the time of cutting the specimen and the tensile stress (300% modulus) at 300% elongation. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester to obtain tensile strength and tensile stress value (300% modulus) at 300% elongation. Each physical property value is shown in Table 2 based on the numerical value of Comparative Example 1 as 100, and indicates that the higher the numerical value, the better.
  • 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 measuring temperature (0 ° C. to 60 ° C.) in a torsion mode.
  • the Payne effect ( ⁇ G ′) is expressed as the difference between the minimum and maximum values of 0.07% to 40% of the strain, and the smaller the Payne effect, the better the dispersibility of the filler.
  • the higher the tan ⁇ at low temperature 0 ° C. the better the braking performance on wet road surfaces.
  • the lower the high temperature 60 ° C. tan ⁇ the lower the hysteresis loss and the lower the cloud resistance (fuel efficiency).
  • Each physical property value is shown in Table 2 based on the numerical value of Comparative Example 1 as 100, and indicates that the higher the numerical value, the better.
  • the modified styrene-butadiene copolymers of Examples 1 to 4 prepared by using the modified initiator composition and the aminosilane-based compound prepared using the substituted styrene-based compound according to the present invention Molded article (test piece) prepared from a rubber composition comprising a shows a significantly reduced value in the Penny effect ( ⁇ G ') compared to the molded article prepared from a rubber composition comprising the unmodified styrene-butadiene copolymer of Comparative Example 1 It was confirmed.
  • the dispersibility of the silica (filler) in the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 to 4 according to the present invention is superior to that of the silica in the rubber composition of Comparative Example 1.
  • the modified styrene-butadiene copolymers of Examples 1 to 4 according to the present invention show excellent affinity with the filler, and the modifications of Examples 1 to 4 according to one embodiment of the present invention. It can be seen that filler affinity functional groups are present in the styrene-butadiene copolymer.
  • the modified styrene-butadiene copolymer according to the embodiment of the present invention is modified by the aminosilane-based compound of Formula 1 and the substituted styrene-based compound of Formula 2, thereby preventing the amino of Formula 1 in the copolymer.
  • the filler affinity functional group derived from the silane compound and the substituted styrene compound of the formula (2) is introduced.
  • the rubber composition comprising the unmodified styrene-butadiene copolymer of Comparative Example 1 also in tensile strength, 300% modulus, braking resistance to wet road surface (0 ° C. tan ⁇ ) and low cloud resistance (60 ° C. tan ⁇ ).
  • the molded articles prepared from the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 to 4 were significantly improved compared to the molded articles prepared from the examples.
  • the molded article prepared from the rubber composition comprising the modified styrene-butadiene copolymer of Comparative Example 2 and Comparative Example 3, which is modified but does not use the modified initiator composition prepared using the substituted styrene-based compound according to the present invention respectively Tensile strength, 300% modulus, and braking resistance (0 ° C. tan ⁇ ) and low cloud resistance compared to molded articles prepared from the rubber compositions comprising the modified styrene-butadiene copolymers of Examples 1 and 4 60 ° C. tan ⁇ ) decreased significantly.
  • the rubber composition comprising the modified styrene-butadiene copolymer of Comparative Example 4 prepared using a compound other than the aminosilane-based compound according to the present invention as a modifier and the molded article prepared therefrom are modified styrene- of Example 1

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Abstract

La présente invention concerne un polymère à base de diène conjugué contenant un groupe fonctionnel dérivé d'un composé à base de styrène substitué et un groupe fonctionnel dérivé d'un composé à base d'aminosilane ; l'invention concerne également un procédé pour sa préparation et une composition de caoutchouc contenant celui-ci. Le polymère à base de diène conjugué modifié obtenu contient, sur les deux extrémités de la chaîne principale, un groupe fonctionnel dérivé d'un composé à base d'aminosilane de formule chimique 1 et un groupe fonctionnel dérivé d'un composé à base de styrène substitué de formule chimique 2, présentant ainsi un rapport de modification élevé, et présentant une excellente affinité pour une charge lorsqu'il est appliqué à une composition de caoutchouc. En conséquence, le polymère à base de diène conjugué modifié peut empêcher la coagulation de la charge dans la composition de caoutchouc et augmenter la dispersibilité de la charge, améliorant ainsi l'aptitude au traitement de la composition de caoutchouc.
PCT/KR2017/004114 2016-04-25 2017-04-17 Polymère à base de diène conjugué modifié et procédé de préparation associé WO2017188641A2 (fr)

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US15/761,320 US10533062B2 (en) 2016-04-25 2017-04-17 Modified conjugated diene-based polymer and method for preparing the same
EP17789826.9A EP3333199B1 (fr) 2016-04-25 2017-04-17 Polymère à base de diène conjugué modifié et procédé de préparation associé
CN201780003390.XA CN108350118B (zh) 2016-04-25 2017-04-17 改性共轭二烯类聚合物及其制备方法
JP2018522735A JP6651621B2 (ja) 2016-04-25 2017-04-17 変性共役ジエン系重合体およびその製造方法
CN202010514552.XA CN111763274B (zh) 2016-04-25 2017-04-17 改性共轭二烯类聚合物及其制备方法

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JP2020533459A (ja) * 2018-05-08 2020-11-19 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
JP2021505712A (ja) * 2017-12-05 2021-02-18 エルジー・ケム・リミテッド 変性共役ジエン系重合体及びこれを含むゴム組成物
WO2021107434A1 (fr) * 2019-11-29 2021-06-03 주식회사 엘지화학 Agent de modification, et polymère de diène conjugué modifié produit à l'aide de celui-ci
RU2826755C1 (ru) * 2019-11-29 2024-09-16 ЭлДжи КЕМ, ЛТД. Модифицирующий агент и модифицированный сопряженный диеновый полимер, полученный с его применением

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JP2020516739A (ja) * 2017-12-05 2020-06-11 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
JP2021505712A (ja) * 2017-12-05 2021-02-18 エルジー・ケム・リミテッド 変性共役ジエン系重合体及びこれを含むゴム組成物
US11299559B2 (en) 2017-12-05 2022-04-12 Lg Chem, Ltd. Modified conjugated diene-based polymer and rubber composition including the same
JP7462557B2 (ja) 2017-12-05 2024-04-05 エルジー・ケム・リミテッド 変性共役ジエン系重合体及びこれを含むゴム組成物
JP2020533459A (ja) * 2018-05-08 2020-11-19 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
US11485800B2 (en) 2018-05-08 2022-11-01 Lg Chem, Ltd. Modified conjugated diene-based polymer and rubber composition including the same
WO2021107434A1 (fr) * 2019-11-29 2021-06-03 주식회사 엘지화학 Agent de modification, et polymère de diène conjugué modifié produit à l'aide de celui-ci
RU2826755C1 (ru) * 2019-11-29 2024-09-16 ЭлДжи КЕМ, ЛТД. Модифицирующий агент и модифицированный сопряженный диеновый полимер, полученный с его применением
US12202922B2 (en) 2019-11-29 2025-01-21 Lg Chem, Ltd. Modifying agent and modified conjugated diene polymer prepared by using the same

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