WO2017111499A1 - Composé polymère, procédé de préparation d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié - Google Patents

Composé polymère, procédé de préparation d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié Download PDF

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Publication number
WO2017111499A1
WO2017111499A1 PCT/KR2016/015106 KR2016015106W WO2017111499A1 WO 2017111499 A1 WO2017111499 A1 WO 2017111499A1 KR 2016015106 W KR2016015106 W KR 2016015106W WO 2017111499 A1 WO2017111499 A1 WO 2017111499A1
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Prior art keywords
formula
groups
polymer
conjugated diene
carbon atoms
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English (en)
Korean (ko)
Inventor
손해성
이희승
김노마
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020160176016A external-priority patent/KR101880370B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2018506535A priority Critical patent/JP6652633B2/ja
Priority to US15/749,195 priority patent/US10829627B2/en
Priority to EP16879366.9A priority patent/EP3312205B1/fr
Priority to CN201680052576.XA priority patent/CN108026222B/zh
Publication of WO2017111499A1 publication Critical patent/WO2017111499A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a polymer compound useful as a polymer modifier, a modified conjugated diene polymer including a functional group derived therefrom, and a method for producing a modified conjugated diene polymer using the polymer compound.
  • 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.
  • a repulsive elasticity of 50 ° C. to 80 ° C., tan ⁇ , Goodrich heat generation and the like are used as an evaluation index of the vulcanized rubber. 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 adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final SBR or BR rubber, and the movement of the chain ends by the binding or modification of the chain ends and the binding force with fillers such as silica or carbon black can be increased. Is widely used as a rubber material for tires.
  • 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.
  • 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.
  • silica is used as reinforcing fillers, low hysteresis loss and wet skid 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.
  • the present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a polymer compound for rubber modifier that can provide a functional group as desired.
  • Another object of the present invention is to provide a modified conjugated diene-based polymer comprising the functional group derived from the high molecular compound.
  • Still another object of the present invention is to provide a method for producing a modified conjugated diene-based polymer using the polymer compound for rubber modifiers.
  • the present invention provides a polymer compound comprising a structural unit represented by the formula (1).
  • X 1 , X 2 , X 3 and X 4 are independently unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70
  • a 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a high molecular compound comprising a structural unit represented by the following formula (1).
  • X 1 , X 2 , X 3 and X 4 are independently unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70
  • a 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the present invention comprises the steps of 1) polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent to prepare an active polymer having an alkali metal bonded to at least one end; 2) obtaining a first modified polymer by reacting the active polymer with a high molecular compound comprising a structural unit represented by Formula 1 below; And 3) it provides a method for producing a modified conjugated diene-based polymer comprising the step of reacting the first modified polymer with a silane compound.
  • X 1 , X 2 , X 3 and X 4 are independently unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70
  • a 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the polymer compound including the structural unit represented by Formula 1 according to the present invention may be used as a modifier for rubber, in particular, a conjugated diene polymer, and may be bonded to the conjugated diene polymer chain to provide a functional group.
  • the modified conjugated diene-based polymer according to the present invention is excellent in affinity with fillers, particularly silica fillers, by combining a polymer compound-derived functional group and a silane-based compound-derived functional group in the polymer chain comprising a structural unit represented by the formula (1).
  • the amine groups included in the polymer itself may reduce toxic components that may occur when manufacturing a processed product (eg, a tire).
  • the production method according to the present invention can easily prepare a modified conjugated diene-based polymer having excellent modification rate by using a high molecular compound containing a structural unit represented by the formula (1).
  • the manufacturing method reacts the polymer compound containing the structural unit represented by the formula (1) with the active polymer, and then continuously reacted with the silane compound, thereby improving affinity with the silica-based filler as compared to the general modified conjugated diene-based polymer. Significantly improved to improve processability.
  • the rubber composition according to the present invention may be excellent in workability by including a modified conjugated diene-based polymer having excellent affinity with the filler, and as a result, the processed product manufactured using the rubber composition is tensile strength, wear resistance and wet Road resistance properties may be excellent.
  • the present invention provides a polymer compound for rubber modifiers capable of providing a plurality of functional groups.
  • the polymer compound according to an embodiment of the present invention is characterized by including a structural unit represented by the following Chemical Formula 1.
  • X 1 , X 2 , X 3 and X 4 are independently unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70
  • a 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the polymer compound may be a compound including a plurality of functional group-containing derived units such as X 1 , X 2 , X 3 and X 4 bonded to the main chain as shown in Formula 1, and the plurality of functional groups
  • a functional group By having a containing derived unit, when using it as a polymer modifier, a functional group can be provided as desired.
  • the polymer compound may be a block copolymer in which each repeating unit having a molar ratio of m, n, o, and p forms a block, or a random copolymer in which the repeating units are arranged randomly.
  • derived substituent and “derived unit” may refer to a structure derived from a substance, a substance, a functional group derived from the substance, or the substance itself, and for example, a compound derived substituent including a nitrile group includes a nitrile group.
  • the compound itself may include a structure, a functional group, and a nitrile group generated from the compound.
  • X 1 , X 2 , X 3 and X 4 are each independently a halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
  • a substituent derived from a compound specifically, at least one of X 1 , X 2 , X 3 and X 4 may be substituted with halogen.
  • X 1 may be an alkyl group, ester group or alkylaryl group having 1 to 10 carbon atoms substituted with halogen.
  • X 2 may be an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.
  • X 3 may be represented by the following Chemical Formula 2.
  • R 1 is an ester group
  • R 2 is an alkyl group having 1 to 20 carbon atoms
  • a is an integer of 0 to 10.
  • R 1 is an ester group
  • R 2 is an alkyl group having 1 to 20 carbon atoms
  • a may be an integer of 0 to 3. More specifically, when b is 0 in Formula 2, R 1 is an ester group, R 2 is an alkyl group having 6 to 20 carbon atoms, when b is not 0, R 1 is an ester group, R 2 May be an alkyl group having 1 to 6 carbon atoms.
  • R 1 may be a portion that bonds with the main chain of the polymer compound.
  • X 4 may be represented by the following Chemical Formula 3.
  • R 3 is an alkylene group having 1 to 6 carbon atoms, an ester group or an arylene group having 6 to 10 carbon atoms,
  • R 4 and R 5 are each independently an alkyl group having 1 to 10 carbon atoms, or are connected to each other to form a ring structure having 3 to 10 carbon atoms,
  • b is an integer of 1-8.
  • R 3 may be an arylene group having 6 to 10 carbon atoms, and R 4 and R 5 may be each independently an alkyl group having 1 to 6 carbon atoms.
  • R 3 may be a portion that bonds with the main chain of the polymer compound.
  • the polymer compound including the structural unit represented by Chemical Formula 1 may include a structural unit represented by the following Chemical Formula 4 or Chemical Formula 5.
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70.
  • polymer compound including the structural unit represented by Formula 1 may be a rubber modifier.
  • the polymer compound including the structural unit represented by Formula 1 may be a modifier for a conjugated diene polymer.
  • the conjugated diene polymer may be a conjugated diene homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
  • the present invention provides a modified conjugated diene-based polymer prepared from the above production method.
  • 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 a high molecular compound comprising a structural unit represented by the following formula (1).
  • X 1 , X 2 , X 3 and X 4 are independently unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70
  • a 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • polymer compound including the structural unit represented by Chemical Formula 1 is as described above.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared through the production method described below, may include a functional group derived from a polymer compound including a structural unit represented by the formula (1).
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may include a functional group derived from a silane-based compound.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may be represented by the following formula (6) or formula (7).
  • Poly represents a polymer chain
  • n, o 1 , o 2 and p represent the molar ratio of each repeating unit, m + n + o 1 + o 2 + p is 100, m, n, p are as described above, o 1 + o 2 is 1 to 50,
  • o 1 is 0 to 49 and o 2 is 1 to 50.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention is a polymer compound-derived functional group and a silane-based compound-derived functional group including the structural unit represented by the formula (1) is combined to affinity with the filler, in particular silica-based filler
  • affinity with the silica-based filler may be remarkably improved as compared with the general modified conjugated diene-based polymer. Therefore, the processability of the rubber composition including the modified conjugated diene-based polymer may be excellent, and as a result, the tensile strength, wear resistance, and wet road resistance of a molded article manufactured using the rubber composition may be improved.
  • the modified conjugated diene-based polymer may be an amine group is bonded, it is possible to reduce the generation of toxic components compared to injecting the amine component separately when manufacturing a molded article, such as a tire through the rubber composition using the same.
  • the modified conjugated diene-based polymer may include a silane group of 100 ppm to 10,000 ppm relative to the total weight of the polymer.
  • the content of the silane group is a value obtained by analyzing silicon (Si) in the polymer through ICP (Inductively Coupled Plasma) analysis.
  • the modified conjugated diene-based polymer may have a number average molecular weight of 10,000 g / mol to 1,000,000 g / mol, specifically, may be 100,000 g / mol to 700,000 g / mol.
  • the modified conjugated diene-based polymer may have a weight average molecular weight of 100,000 g / mol to 2,000,000 g / mol, specifically, may be 200,000 g / mol to 1,500,000 g / mol.
  • the modified conjugated diene-based polymer may have a molecular weight distribution of 1.0 to 3.0, specifically 1.5 to 2.5.
  • the weight average molecular weight and the number average molecular weight are polystyrene equivalent molecular weights respectively analyzed by gel permeation chromatography (GPC), and the molecular weight distribution (Mw / Mn) is also called polydispersity, and the weight average molecular weight (Mw) And the ratio (Mw / Mn) to the number average molecular weight (Mn).
  • GPC gel permeation chromatography
  • the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% by weight to 50% by weight, and the glass transition temperature when the vinyl content is in the above range. Can be adjusted to an appropriate range, and when applied to a tire, not only the properties required for the tire such as driving resistance and braking force are excellent, but also it has an effect of reducing fuel consumption.
  • the vinyl content represents the content of the 1,2-added conjugated diene monomer instead of 1,4-addition based on 100% by weight of the conjugated diene polymer composed of a monomer having a vinyl group or a conjugated diene monomer.
  • the modified conjugated diene-based polymer may be prepared by the manufacturing method described below, may be a conjugated diene monomer homopolymer or a copolymer of a vinyl aromatic monomer and a conjugated diene monomer, when the polymer is a copolymer
  • the aromatic vinyl monomer-derived substituent may be included in less than 50% by weight.
  • the present invention also provides a method for producing a modified conjugated diene-based polymer using a high molecular compound.
  • the production method 1) polymerized conjugated diene monomer or aromatic vinyl monomer and conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent, the alkali metal is bonded to at least one end Preparing an active polymer (step 1); 2) obtaining a first modified polymer by reacting the active polymer with a high molecular compound including a structural unit represented by the following Chemical Formula 1 (step 2); And 3) reacting the first modified polymer with a silane compound (step 3).
  • X 1 , X 2 , X 3 and X 4 are independently unsubstituted or substituted with one or more substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • substituents selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms
  • n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
  • n 1 to 50
  • n is from 0 to 50
  • o is from 1 to 50
  • p 1 to 70
  • a 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • polymer compound including the structural unit represented by Chemical Formula 1 is as described above.
  • Method for producing a modified conjugated diene-based polymer comprises the step of reacting the polymer compound comprising a structural unit represented by the formula (1) with the active polymer, and subsequently with the silane-based compound, Since the modified conjugated diene-based polymer may include a silane group which is not bonded to a conjugated diene-based polymer, for example, a styrene-butadiene copolymer chain, the affinity with silica may be further improved as compared with a general modified conjugated diene-based polymer.
  • step 1 is a step for preparing an active polymer having an alkali metal bonded to at least one end thereof, wherein a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer are present in a hydrocarbon solvent in the presence of an organic alkali metal compound.
  • the polymerization of step 1 may be to use a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer as a monomer. That is, the polymer prepared by the method according to an embodiment of the present invention may be a polymer derived from a conjugated diene monomer or a copolymer derived from an aromatic vinyl monomer and a conjugated diene monomer.
  • the copolymer may be a random copolymer.
  • the "random copolymer” may indicate that the structural units constituting the copolymer are randomly arranged.
  • 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 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 conjugated diene-based monomer is 60% by weight or more of the unit derived from the conjugated diene-based monomer in the finally prepared modified conjugated diene-based polymer.
  • it may be used in an amount of 60 wt% to 90 wt%, more specifically 60 wt% to 85 wt%.
  • 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.
  • 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 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, lithium isopropy
  • the polymerization of step 1 may be performed by further adding a polar additive as needed, the polar additive may be added to 0.001 parts by weight to 10 parts by weight based on 100 parts by weight of the total monomer. Specifically, the content may be added in an amount of 0.001 part by weight to 1 part by weight, more specifically 0.005 part by weight to 0.1 part by weight, based on 100 parts by weight of the total monomers.
  • the polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis It may be one or more selected from the group consisting of (3-dimethylaminoethyl) 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 1 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 2 is a step of reacting the active polymer with a high molecular compound including a structural unit represented by Chemical Formula 1 to prepare a first modified polymer.
  • the prepared first modified polymer may be one in which a functional group derived from a polymer compound including the structural unit represented by Formula 1 is bonded to one end of a conjugated diene-based polymer chain.
  • the polymer compound including the structural unit represented by Chemical Formula 1 may be used in a ratio of 0.1 mol to 10 mol with respect to 1 mol of the organic alkali metal compound.
  • the reaction of step 2 is a modification reaction for introducing a functional group into the polymer, the reaction may be performed for 10 minutes to 5 hours in the temperature range of 10 °C to 120 °C.
  • the preparation 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 2 above.
  • step 3 can maximize the affinity with the silica compound by reacting the silane-based compound with the first modified polymer obtained in step 2.
  • the silane-based compound may include a silane group not bonded to the polymer chain in the polymer by binding to a halogen element in the polymer without binding to the conjugated diene-based polymer chain in the first modified polymer. Therefore, the affinity with silica can be improved compared with the general modified conjugated diene-based polymer.
  • the reaction may be performed for 10 minutes to 5 hours in a temperature range of 10 °C to 120 °C.
  • the method for preparing the modified conjugated diene-based polymer of the present invention may be, for example, a continuous polymerization method including one or two or more reactors.
  • the silane compound is vinyl chlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, p-styryl trimethoxy silane, 3-methacryloxy propyl triethoxy silane , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethy
  • the silane-based compound may be used in a ratio of 0.001 mol to 10 mol, specifically 0.001 mol to 5 mol, more specifically 0.005 mol to 1 mol relative to 1 mol of the polymer compound. have.
  • modified conjugated diene-based polymer manufacturing method may be performed through the steps as shown in Scheme 1.
  • SBR represents a styrene-butadiene copolymer chain
  • m, n, o, o 1 , o 2 and p are as described above.
  • the preparation method according to an embodiment of the present invention is to prepare a styrene-butadiene copolymer and then reacted with a polymer compound (Scheme 1 in 1) comprising a structural unit represented by the formula (1)
  • a modified conjugated diene-based polymer represented by 3 is prepared by preparing a compound containing the structural unit represented by 2 (Scheme 1 to 2) and reacting with a silane-based compound (for example, 3-aminopropyltrimethoxysilane) Scheme 1 to 3) may be prepared.
  • the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
  • the rubber composition according to an embodiment of the present invention may be a modified conjugated diene-based polymer containing 10 wt% or more, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt%. have. If the content of the modified conjugated diene-based polymer is less than 10% by weight, the effect of improving the wear resistance and crack resistance of a molded article, for example, a tire manufactured using the rubber composition 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 polymer may be included in an amount of 1 part by weight to 90 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 to 200 parts by weight of a filler with respect to 100 parts by weight of the modified conjugated diene-based polymer, the filler may be a silica-based filler, carbon black-based filler or a combination thereof.
  • 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 high affinity with a silica-based filler as an active moiety is used as the 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 components described above, various additives commonly used in the rubber industry, specifically, 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 said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. 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 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 manufactured using the rubber composition.
  • the tire may include a tire or a tire tread.
  • a denaturant B was prepared, including a structural unit represented by i), wherein m is 15, n is 35, o is 32, and p is 18.
  • a denaturant C was prepared, which comprises a structural unit represented by i), wherein m is 8, n is 34, o is 32, and p is 26.
  • a denaturant D which is a polymer compound containing the structural unit represented by ii), was prepared.
  • molecular weight analysis was determined by GPC analysis under 40 ° C conditions.
  • 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
  • the reaction was stopped using isopropyl alcohol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added.
  • BHT butylated hydroxytoluene
  • the resulting polymer was poured into hot water heated with steam, stirred to remove the solvent, and then dried by roll to remove residual solvent and water to prepare a modified styrene-butadiene copolymer.
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that 32.8 g of the modifying agent B prepared in Preparation Example 2 was used instead of the modifying agent A.
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that 32.8 g of the modifying agent C prepared in Preparation Example 3 was used instead of the modifying agent A.
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that 32.8 g of the modified D prepared in Preparation Example 4 was used instead of the modifying agent A.
  • a styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 1, except that 2.8 g of tetrachlorosilane 10 wt% normal hexane solution was used as the coupling agent instead of the denaturant A.
  • Example 2 Same method as in Example 1, except that 11.3 g of a 10 wt% solution of 3- (N, N-dimethylamino) propyl trimethoxysilane was used instead of the denaturant A. Modified styrene-butadiene copolymer was prepared through.
  • SM Styrene derived units
  • the weight average molecular weight (Mw, g / mol), the number average molecular weight (Mn, g / mol) and the maximum peak molecular weight (Mp, g / mol) were measured by GPC analysis under 40 ° C, and the molecular weight distribution (Mw / Mn ) Is calculated as the ratio of the measured weight average molecular weight and the number average molecular weight, and the number of couplings (Mp1 / Mp2) is the value obtained by dividing the maximum peak molecular weight after modification (Mp1) and the maximum peak molecular weight before modification (Mp2), respectively.
  • 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
  • Mooney viscosity of each copolymer (MV, (ML1 + 4, @ 100 °C) was measured using a Rotor Speed 2 ⁇ 0.02 rpm, Large Rotor 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, filled into the die cavity, platen was operated, preheated at 100 °C for 1 minute, and measured for 4 minutes.
  • the silicon content of each copolymer was measured using ICP-OES Optima8 300 DV (Perkin Elmer).
  • Example 1 24 46 54 34 1.6 2.4 70 523
  • Example 2 25 47 54 32 1.7 2.6 69 762
  • Example 3 25 46 61 34 1.8 2.5 74 369
  • Example 4 25 46 51 32 1.6 2.2 64 283
  • Comparative Example 1 24 46 56 35 1.6 2.4 71 ⁇ 10 Comparative Example 2 24 45 59 37 1.6 2.4 74 56 Comparative Example 3 24 46 45 32 1.4 1.8 56 145
  • Coupling number in Table 2 indicates that the polymer chain is coupled or modified by the modifier, the larger the number indicates that the coupling or denaturation was made at a higher ratio.
  • Each rubber composition was prepared through a first stage kneading, a second stage kneading and a third stage kneading. At this time, the amount of the substance except the modified conjugated diene copolymer is shown based on 100 parts by weight of the modified conjugated diene 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
  • Mooney Viscosity (MV, (ML1 + 4, @ 100 ° C)) is a Rotor Speed 2 ⁇ 0.02 rpm using ALPHA Technologies, Inc. MV-2000, primary blend (single kneading) and secondary blend using Large Rotor (2 stage kneading), respectively, and the samples used were allowed to stand at room temperature (23 ⁇ 3 °C) for more than 30 minutes, and then collected 27 ⁇ 3 g, filled in the die cavity, and platen operated at 100 °C. Preheat for 1 minute and then measure for 4 minutes.
  • 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 Machine 4204 (Instron Co., Ltd.) tensile tester to obtain a tensile strength and tensile stress value at 300% elongation.
  • Viscoelastic properties were measured by using a dynamic mechanical analyzer (TA Co., Ltd.) in a torsion mode by changing the strain at a frequency of 10 Hz and measuring temperature (0 ° C. to 60 ° C.).
  • the higher the Tan ⁇ at low temperature 0 ° C. the better the braking performance.
  • the lower the high temperature 60 ° C. Tan ⁇ the lower the hysteresis loss, and the lower the cloud resistance (fuel efficiency).
  • the resulting value was expressed as an index value based on the measured value of the rubber composition including the copolymer of Comparative Example 3 based on 100, which means that it is excellent as the index value increases.
  • the rubber composition comprising the conjugated diene-based polymer of Comparative Example 1 and Comparative Example 2 in which the rubber composition comprising the modified styrene-butadiene copolymer of Examples 1 to 4 according to an embodiment of the present invention is unmodified It is confirmed that it shows improved performance in all aspects such as resistance against wet roads, fuel efficiency, and mechanical properties.
  • the specimen prepared from the rubber composition comprising the modified styrene-butadiene copolymer of Examples 1 to 4 according to an embodiment of the present invention is unmodified or modified styrene-butadiene air of Comparative Examples 1 to 3
  • the powder of silica in the rubber composition comprising the modified styrene-butadiene copolymer of Examples 1 to 4 It can be seen that the acidity is superior to the dispersibility of silica in the rubber compositions of Comparative Examples 1 to 3. This indicates that the modified styrene-butadiene copolymers of Examples 1 to 4 according to one embodiment of the present invention have excellent silicide, ie, affinity with filler.

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Abstract

La présente invention concerne : un composé polymère utile comme modificateur de polymère ; un polymère à base de diène conjugué modifié comprenant un groupe fonctionnel dérivé de ce dernier ; et un procédé de préparation d'un polymère à base de diène conjugué modifié mettant en œuvre le composé polymère. Selon la présente invention, un composé modificateur de caoutchouc est utilisé comme modificateur de caoutchouc, notamment comme modificateur d'un polymère à base de diène conjugué, de sorte à être couplé à la chaîne du polymère à base de diène conjugué, permettant ainsi à un groupe fonctionnel présentant une affinité de remplissage d'être facilement introduit.
PCT/KR2016/015106 2015-12-24 2016-12-22 Composé polymère, procédé de préparation d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié Ceased WO2017111499A1 (fr)

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JP2018506535A JP6652633B2 (ja) 2015-12-24 2016-12-22 高分子化合物、これを用いた変性共役ジエン系重合体の製造方法及び変性共役ジエン系重合体
US15/749,195 US10829627B2 (en) 2015-12-24 2016-12-22 Polymer compound, method for preparing modified and conjugated diene-based polymer using the same, and modified and conjugated diene-based polymer
EP16879366.9A EP3312205B1 (fr) 2015-12-24 2016-12-22 Composé polymère, procédé de préparation d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié
CN201680052576.XA CN108026222B (zh) 2015-12-24 2016-12-22 聚合物化合物、使用其制备改性共轭二烯类聚合物的方法以及改性共轭二烯类聚合物

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US11560442B2 (en) 2017-04-10 2023-01-24 Synthomer Adhesive Technologies Llc Functionalized resin having a polar linker
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CN114174350A (zh) * 2019-08-06 2022-03-11 旭化成株式会社 共轭二烯系聚合物、支化剂、共轭二烯系聚合物的制造方法、充油共轭二烯系聚合物、橡胶组合物以及轮胎
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CN114174350B (zh) * 2019-08-06 2024-04-30 旭化成株式会社 共轭二烯系聚合物及其制造方法、充油共轭二烯系聚合物、橡胶组合物以及轮胎
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