WO2017111499A1 - Polymer compound, method for preparing modified conjugated diene-based polymer by using same, and modified conjugated diene-based polymer - Google Patents

Polymer compound, method for preparing modified conjugated diene-based polymer by using same, and modified conjugated diene-based polymer 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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formula
groups
polymer
conjugated diene
carbon atoms
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PCT/KR2016/015106
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French (fr)
Korean (ko)
Inventor
손해성
이희승
김노마
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주식회사 엘지화학
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Priority claimed from KR1020160176016A external-priority patent/KR101880370B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16879366.9A priority Critical patent/EP3312205B1/en
Priority to US15/749,195 priority patent/US10829627B2/en
Priority to JP2018506535A priority patent/JP6652633B2/en
Priority to CN201680052576.XA priority patent/CN108026222B/en
Publication of WO2017111499A1 publication Critical patent/WO2017111499A1/en

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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

The present invention relates to: a polymer compound useful as a polymer modifier; a modified conjugated diene-based polymer comprising a functional group derived therefrom; and a method for preparing a modified conjugated diene-based polymer by using the polymer compound. According to the present invention, a rubber modifier compound is used as a modifier for rubber, particularly, as a modifier for a conjugated diene-based polymer, so as to be coupled to the chain of the conjugated diene-based polymer, thereby enabling a filler affinic functional group to be readily introduced.

Description

고분자 화합물, 이를 이용한 변성 공액디엔계 중합체의 제조방법 및 변성 공액디엔계 중합체Polymer compound, preparation method of modified conjugated diene polymer and modified conjugated diene polymer
[관련출원과의 상호인용][Citations with Related Applications]
본 출원은 2015.12.24자 한국 특허 출원 제10-2015-0186340호 및 2016.12.21자 한국 특허 출원 제10-2016-0176016에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된　모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0186340, issued on December 24, 2015 and Korean Patent Application No. 10-2016-0176016, issued on December 21, 2016. Is included as part of this specification.
[기술분야][Technical Field]
본 발명은 중합체 변성제로 유용한 고분자 화합물, 이의 유래 작용기를 포함하는 변성 공액디엔계 중합체 및 상기 고분자 화합물을 이용한 변성 공액디엔계 중합체의 제조방법에 관한 것이다.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.
최근 자동차에 대한 저연비화의 요구에 따라, 타이어용 고무 재료로서 구름 저항이 적고, 내마모성, 인장 특성이 우수하며, 웨트 스키드 저항으로 대표되는 조정 안정성도 겸비한 공액디엔계 중합체가 요구되고 있다. In recent years, with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low rolling resistance, excellent wear resistance and tensile properties, and adjusting stability represented by wet skid resistance.
타이어의 구름 저항을 감소시키기 위해서는 가황 고무의 히스테리시스 손실을 작게 하는 방안이 있으며, 이러한 가황 고무의 평가 지표로서는 50℃ 내지 80℃의 반발탄성, tan δ, 굿리치 발열 등이 이용된다. 즉, 상기 온도에서의 반발탄성이 크거나 tan δ 또는 굿리치 발열이 작은 고무 재료가 바람직하다.In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, a repulsive elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heat generation and the like are used. That is, a rubber material having a high rebound elasticity at the above temperature or a small tan δ or good rich heat generation is preferable.
히스테리시스 손실이 작은 고무 재료로서는, 천연 고무, 폴리이소프렌 고무 또는 폴리부타디엔 고무 등이 알려져 있지만, 이들은 웨트 스키드 저항성이 작은 문제가 있다. 이에 최근에는 스티렌-부타디엔 고무(이하, SBR이라 함) 또는 부타디엔 고무(이하, BR이라 함)와 같은 공액디엔계 (공)중합체가 유화중합이나 용액중합에 의해 제조되어 타이어용 고무로서 이용되고 있다. 이 중, 유화중합에 비해 용액중합이 갖는 최대의 장점은 고무 물성을 규정하는 비닐 구조 함량 및 스티렌 함량을 임의로 조절할 수 있고, 커플링(coupling)이나, 변성(modification) 등에 의해 분자량 및 물성 등을 조절할 수 있다는 점이다. 따라서, 최종 제조된 SBR 이나 BR 고무의 구조 변화가 용이하고, 사슬 말단의 결합이나 변성으로 사슬 말단의 움직임을 줄이고 실리카 또는 카본블랙 등의 충진제와의 결합력을 증가시킬 수 있어 용액 중합에 의한 SBR 고무가 타이어용 고무 재료로 많이 사용된다. As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low wet skid resistance. Recently, 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. . Among them, 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.
이러한 용액중합 SBR이 타이어용 고무 재료로 사용되는 경우 상기 SBR 내의 비닐 함량을 증가시킴으로써 고무의 유리전이온도를 상승시켜 주행저항 및 제동력과 같은 타이어 요구 물성을 조절할 수 있을 뿐만 아니라, 유리전이온도를 적절히 조절함으로써 연료소모를 줄일 수 있다. When the solution-polymerized SBR is 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.
상기 용액중합 SBR은 음이온 중합 개시제를 사용하여 제조하며, 형성된 중합체의 사슬 말단을 여러 가지 변성제를 이용하여 결합시키거나, 변성시켜 사용되고 있다. 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.
예를 들어, 미국특허 제4,397,994호에는 일관능성 개시제인 알킬리튬을 이용하여 비극성 용매하에서 스티렌-부타디엔을 중합하여 얻어진 중합체의 사슬 말단의 활성 음이온을 주석화합물과 같은 결합제를 사용하여 결합시킨 기술을 제시하였다. 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.
한편, 타이어 트레드의 보강성 충진제로서 카본블랙 및 실리카 등이 사용되고 있는데, 보강성 충진제로서 실리카를 이용하는 경우 저히스테리시스 손실성 및 웨트 스키드 저항성이 향상된다는 장점이 있다. 그러나, 소수성 표면의 카본블랙 대비 친수성 표면의 실리카는 고무와의 친화성이 낮아 분산성이 나쁘다는 결점을 가지고 있어, 분산성을 개선시키거나 실리카-고무 간의 결합 부여를 행하기 위해 별도의 실란 커플링제를 사용할 필요가 있다. Meanwhile, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as reinforcing fillers, low hysteresis loss and wet skid resistance are improved. However, 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.
이에, 고무 분자 말단부에 실리카와의 친화성이나 반응성을 갖는 관능기를 도입하는 방안이 이루어지고 있으나, 그 효과가 충분하지 않은 실정이다.Thus, a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal portion, but the effect is not sufficient.
따라서, 실리카를 비롯한 충진제와의 친화성이 높은 고무의 개발이 필요한 실정이다.Therefore, there is a need for development of a rubber having high affinity with fillers including silica.
본 발명은 상기 종래기술의 문제점을 해결하기 위하여 안출된 것으로, 목적하는 바에 따른 관능기를 제공할 수 있는 고무 변성제용 고분자 화합물을 제공하는 것을 목적으로 한다. 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.
본 발명의 다른 목적은 상기 고분자 화합물 유래 작용기를 포함하는 변성 공액디엔계 중합체를 제공하는 것이다. 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.
본 발명의 또 다른 목적은 상기 고무 변성제용 고분자 화합물을 이용한 변성 공액디엔계 중합체의 제조방법을 제공하는 것이다. 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.
상기의 과제를 해결하기 위하여, 본 발명은 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물을 제공한다.In order to solve the above problems, the present invention provides a polymer compound comprising a structural unit represented by the formula (1).
[화학식 1][Formula 1]
Figure PCTKR2016015106-appb-I000001
Figure PCTKR2016015106-appb-I000001
상기 화학식 1에서, In Chemical Formula 1,
X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이고,p is 1 to 70,
A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
또한, 본 발명은 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기를 포함하는 변성 공액디엔계 중합체를 제공한다. In addition, 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).
[화학식 1][Formula 1]
Figure PCTKR2016015106-appb-I000002
Figure PCTKR2016015106-appb-I000002
상기 화학식 1에서, In Chemical Formula 1,
X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이고,p is 1 to 70,
A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
아울러, 본 발명은 1) 탄화수소 용매 중에서, 유기 알칼리금속 화합물 존재 하에서 공액디엔계 단량체 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 적어도 일 말단에 알칼리 금속이 결합된 활성 중합체를 제조하는 단계; 2) 상기 활성 중합체를 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물과 반응시켜 제1 변성 중합체를 얻는 단계; 및 3) 상기 제1 변성 중합체를 실란계 화합물과 반응시키는 단계를 포함하는 변성 공액디엔계 중합체의 제조방법을 제공한다.In addition, 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.
[화학식 1][Formula 1]
Figure PCTKR2016015106-appb-I000003
Figure PCTKR2016015106-appb-I000003
상기 화학식 1에서, In Chemical Formula 1,
X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이고,p is 1 to 70,
A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
본 발명에 따른 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 고무용 변성제, 특히 공액디엔계 중합체의 변성제로 사용되어, 상기 공액디엔계 중합체 사슬에 결합되어 관능기를 제공할 수 있다. 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.
본 발명에 따른 변성 공액디엔계 중합체는 중합체 사슬에 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기 및 실란계 화합물 유래 작용기가 결합되어 있음으로써 충진제, 특히 실리카계 충진제와의 친화성이 우수할 수 있으며, 중합체 자체에 포함된 아민기에 의해 가공품(예컨대, 타이어) 제조시 발생할 수 있는 유독 성분을 감소시킬 수 있다.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). In addition, the amine groups included in the polymer itself may reduce toxic components that may occur when manufacturing a processed product (eg, a tire).
또한, 본 발명에 따른 제조방법은 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물을 이용함으로써 변성률이 우수한 변성 공액디엔계 중합체를 용이하게 제조할 수 있다. 또한, 상기 제조방법은 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물과 활성 중합체를 반응시킨 후, 연속적으로 실란계 화합물과 반응시킴으로써, 일반 변성 공액디엔계 중합체에 비해 실리카계 충진제와의 친화력을 현저히 향상시켜 가공성을 증진시킬 수 있다. In addition, 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). In addition, 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.
아울러, 본 발명에 따른 고무 조성물은 상기 충진제와의 친화성이 우수한 변성 공액디엔계 중합체를 포함함으로써 가공성이 우수할 수 있으며, 결과적으로 상기 고무 조성물을 이용하여 제조된 가공품은 인장강도, 내마모성 및 젖은 노면 저항성 특성이 우수할 수 있다.In addition, 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.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다. Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
본 명세서 및 청구범위에서 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 발명은 다수의 관능기를 제공할 수 있는 고무 변성제용 고분자 화합물을 제공한다. The present invention provides a polymer compound for rubber modifiers capable of providing a plurality of functional groups.
본 발명의 일 실시예에 따른 상기 고분자 화합물은 하기 화학식 1로 표시되는 구성단위를 포함하는 것을 특징으로 한다. 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.
[화학식 1][Formula 1]
Figure PCTKR2016015106-appb-I000004
Figure PCTKR2016015106-appb-I000004
상기 화학식 1에서, In Chemical Formula 1,
X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이고,p is 1 to 70,
A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다. A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
상기 고분자 화합물은 상기 화학식 1에 나타난 바와 같이 주 사슬에 다수의 관능기 함유 유래단위, 예컨대 X1, X2, X3 및 X4가 결합된 구성단위를 포함하는 화합물일 수 있으며, 상기 다수의 관능기 함유 유래단위를 가지고 있음으로써 이를 고분자 변성제로서 사용할 경우 목적하는 바에 따라 관능기를 제공할 수 있다. 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 By having a containing derived unit, when using it as a polymer modifier, a functional group can be provided as desired.
이때, 상기 고분자 화합물은 m, n, o 및 p의 몰비율을 갖는 각 반복 단위체가 각각 블록(block)을 이루는 블록 공중합체, 또는 각 반복 단위체가 무질서하게 배열된 랜덤 공중합체인 것일 수 있다. In this case, 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.
본 발명에서 사용되는 용어 "유래 치환기" 및 "유래단위"는 어떤 물질로부터 유래된 구조, 물질, 유래된 관능기 또는 그 물질 자체를 나타내는 것일 수 있으며, 예컨대 니트릴기를 포함하는 화합물 유래 치환기는 니트릴기를 포함하는 화합물로부터 발생된 구조, 관능기, 니트릴기를 포함하는 화합물 자체를 나타내는 것일 수 있다. As used herein, the terms “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.
구체적으로는, 상기 화학식 1에서 X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기인 것으로, 구체적으로는, X1, X2, X3 및 X4 중 적어도 하나는 할로겐으로 치환된 것일 수 있다.Specifically, in Formula 1, 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. An alkyl group, an amine group, an ester group, a nitrile group, a benzophenone group, an acryl group, a vinyl group, a styrene group, a styrene acryl group, or an aryl group which is unsubstituted or substituted with one or more substituents selected. As 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.
구체적으로, 본 발명의 일 실시예에 따르면, 상기 화학식 1에서, X1은 할로겐으로 치환된 탄소수 1 내지 10의 알킬기, 에스테르기 또는 알킬아릴기인 것일 수 있다. Specifically, according to one embodiment of the present invention, in Formula 1, X 1 may be an alkyl group, ester group or alkylaryl group having 1 to 10 carbon atoms substituted with halogen.
또한, 상기 화학식 1에서, X2는 탄소수 1 내지 3의 알킬기 또는 탄소수 3 내지 10의 사이클로알킬기로 치환되거나 비치환된 탄소수 6 내지 10의 아릴기인 것일 수 있다. In addition, in Formula 1, 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.
또한, 상기 화학식 1에서 X3는 하기 화학식 2로 표시되는 것일 수 있다. In addition, in Chemical Formula 1, X 3 may be represented by the following Chemical Formula 2.
[화학식 2][Formula 2]
Figure PCTKR2016015106-appb-I000005
Figure PCTKR2016015106-appb-I000005
상기 화학식 2에서, R1은 에스테르기이고, R2는 탄소수 1 내지 20의 알킬기이며, a는 0 내지 10의 정수이다. In 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.
구체적으로, 상기 화학식 2에서 R1은 에스테르기이고, R2는 탄소수 1 내지 20의 알킬기이며, a는 0 내지 3의 정수인 것일 수 있다. 더욱 구체적으로, 상기 화학식 2에서 b가 0인 경우, 상기 R1은 에스테르기이고, R2는 탄소수 6 내지 20의 알킬기이고, b가 0이 아닌 경우, 상기 R1은 에스테르기이고, R2는 탄소수 1 내지 6의 알킬기인 것일 수 있다. 여기에서, 상기 R1은 고분자 화합물의 주 사슬과 결합하는 부분일 수 있다. Specifically, in Formula 2, 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. Here, R 1 may be a portion that bonds with the main chain of the polymer compound.
또한, 상기 화학식 1에서 X4는 하기 화학식 3으로 표시되는 것일 수 있다. In addition, in Chemical Formula 1, X 4 may be represented by the following Chemical Formula 3.
[화학식 3][Formula 3]
Figure PCTKR2016015106-appb-I000006
Figure PCTKR2016015106-appb-I000006
상기 화학식 3에서,In Chemical Formula 3,
R3은 탄소수 1 내지 6의 알킬렌기, 에스테르기 또는 탄소수 6 내지 10의 아릴렌기이고,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,
R4 및 R5는 서로 독립적으로 탄소수 1 내지 10의 알킬기이거나, 서로 연결되어 탄소수 3 내지 10의 고리 구조를 형성하는 것이며,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,
b는 1 내지 8의 정수이다.b is an integer of 1-8.
구체적으로, 상기 화학식 3에서 R3은 탄소수 6 내지 10의 아릴렌기이고, R4 및 R5는 서로 독립적으로 탄소수 1 내지 6의 알킬기인 것일 수 있다. 여기에서, 상기 R3는 고분자 화합물의 주 사슬과 결합하는 부분일 수 있다. Specifically, in Formula 3, 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. Here, R 3 may be a portion that bonds with the main chain of the polymer compound.
더욱 구체적으로, 상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 구성단위를 포함하는 것일 수 있다. More specifically, 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.
[화학식 4][Formula 4]
Figure PCTKR2016015106-appb-I000007
Figure PCTKR2016015106-appb-I000007
[화학식 5][Formula 5]
Figure PCTKR2016015106-appb-I000008
Figure PCTKR2016015106-appb-I000008
상기 화학식 4 및 화학식 5에서,In Chemical Formulas 4 and 5,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이다.p is 1 to 70.
또한, 상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 고무 변성제인 것일 수 있다. In addition, the polymer compound including the structural unit represented by Formula 1 may be a rubber modifier.
구체적으로는, 상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 공액디엔계 중합체용 변성제인 것일 수 있다. 여기에서, 상기 공액디엔계 중합체는 공액디엔계 단독 중합체 또는 공액디엔계 단량체 및 방향족 비닐계 단량체의 공중합체일 수 있다. Specifically, the polymer compound including the structural unit represented by Formula 1 may be a modifier for a conjugated diene polymer. Herein, the conjugated diene polymer may be a conjugated diene homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
또한, 본 발명은 상기 제조방법으로부터 제조된 변성 공액디엔계 중합체를 제공한다. In addition, the present invention provides a modified conjugated diene-based polymer prepared from the above production method.
본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체는 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기를 포함하는 것을 특징으로 한다. 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).
[화학식 1][Formula 1]
Figure PCTKR2016015106-appb-I000009
Figure PCTKR2016015106-appb-I000009
상기 화학식 1에서, In Chemical Formula 1,
X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이고,p is 1 to 70,
A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
구체적인, 상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 전술한 바와 같다.Specifically, the polymer compound including the structural unit represented by Chemical Formula 1 is as described above.
본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체는 후술하는 제조방법을 통하여 제조된 것일 수 있으며, 상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기를 포함하는 것일 수 있다. 또한, 본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체는 실란계 화합물 유래 작용기를 포함하는 것일 수 있다. 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). In addition, 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.
본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체는 하기 화학식 6 또는 화학식 7로 표시되는 것일 수 있다.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).
[화학식 6][Formula 6]
Figure PCTKR2016015106-appb-I000010
Figure PCTKR2016015106-appb-I000010
[화학식 7][Formula 7]
Figure PCTKR2016015106-appb-I000011
Figure PCTKR2016015106-appb-I000011
상기 화학식 6 및 화학식 7에서, In Chemical Formulas 6 and 7,
Poly는 중합체 사슬을 나타내는 것이고,Poly represents a polymer chain,
m, n, o1, o2 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o1+o2+p는 100이고, m, n, p는 전술한 바와 같고, o1+o2는 1 내지 50이고,m, 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,
o1은 0 내지 49이고, o2는 1 내지 50이다.o 1 is 0 to 49 and o 2 is 1 to 50.
본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체는 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기 및 실란계 화합물 유래 작용기가 결합되어 있어 충진제, 특히 실리카계 충진제와의 친화성이 우수할 수 있으며, 특히 상기 실란계 화합물 유래 작용기는 중합체 사슬과 직접적으로 결합되지 않으므로 일반 변성 공액디엔계 중합체에 비해 실리카계 충진제와의 친화력이 현저히 향상될 수 있다. 따라서, 상기 변성 공액디엔계 중합체를 포함하는 고무 조성물의 가공성이 우수할 수 있으며, 결과적으로 상기 고무 조성물을 이용하여 제조된 성형품, 예컨대 타이어의 인장강도, 내마모성 및 젖은 노면 저항성이 개선될 수 있다. 또한, 상기 변성 공액디엔계 중합체는 아민기가 결합되어 있는 것일 수 있으며, 이에 이를 이용한 고무 조성물을 통하여 성형품, 예컨대 타이어를 제조할 시 아민 성분을 별도로 주입하는 것에 비하여 유독성분 발생을 줄일 수 있다. 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 In particular, since the functional group derived from the silane-based compound is not directly bonded to the polymer chain, the 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. In addition, 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.
구체적으로, 상기 변성 공액디엔계 중합체는 중합체 전체 중량 대비 100 ppm 내지 10,000 ppm의 실란기를 포함하는 것일 수 있다. 여기에서, 상기 실란기의 함량은 ICP(Inductively Coupled Plasma) 분석을 통하여 중합체 내 규소(Si)를 분석하고 이로부터 얻어진 값이다.Specifically, 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. Herein, the content of the silane group is a value obtained by analyzing silicon (Si) in the polymer through ICP (Inductively Coupled Plasma) analysis.
또한, 상기 변성 공액디엔계 중합체는 수평균 분자량이 10,000 g/mol 내지1,000,000 g/mol인 것일 수 있으며, 구체적으로는 100,000 g/mol 내지 700,000 g/mol인 것일 수 있다. In addition, 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.
상기 변성 공액디엔계 중합체는 중량평균 분자량이 100,000 g/mol 내지 2,000,000 g/mol인 것일 수 있으며, 구체적으로는 200,000 g/mol 내지 1,500,000 g/mol인 것일 수 있다. 상기 변성 공액디엔계 중합체는 분자량 분포가 1.0 내지 3.0, 구체적으로는 1.5 내지 2.5인 것일 수 있다. 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.
여기에서, 상기 중량평균 분자량 및 수평균 분자량은 각각 겔 투과형 크로마토그래피(GPC)로 분석되는 폴리스티렌 환산 분자량이며, 분자량 분포(Mw/Mn)는 다분산성(polydispersity)이라고도 불리며, 중량평균 분자량(Mw)과 수평균 분자량(Mn)과의 비(Mw/Mn)로 계산하였다.Here, 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).
또한, 상기 변성 공액디엔계 중합체는 비닐 함량이 5 중량% 이상, 구체적으로는 10 중량% 이상, 보다 구체적으로는 10 중량% 내지 50 중량%일 수 있고, 비닐 함량이 상기 범위일 경우 유리전이온도가 적절한 범위로 조절될 수 있어 타이어에 적용 시 주행저항 및 제동력과 같은 타이어에 요구되는 물성이 우수할 뿐 아니라 연료소모를 줄이는 효과가 있다. In addition, 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.
이때, 상기 비닐 함량은 비닐기를 갖는 단량체 또는 공액디엔계 단량체로 이루어진 공액디엔계 중합체 100 중량%에 대하여 1,4-첨가가 아닌 1,2-첨가된 공액디엔계 단량체의 함량을 나타내는 것이다.In this case, 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.
또한, 상기 변성 공액디엔계 중합체는 후술하는 제조방법에 의하여 제조된 것일 수 있으며, 공액디엔계 단량체 단독 중합체이거나 비닐계 방향족 단량체와 공액디엔계 단량체의 공중합체인 것일 수 있고, 상기 중합체가 공중합체인 경우 방향족 비닐계 단량체 유래 치환기를 50 중량% 이하로 포함하는 것일 수 있다.In addition, 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.
또한, 본 발명은 고분자 화합물을 이용한 변성 공액디엔계 중합체의 제조방법을 제공한다.The present invention also provides a method for producing a modified conjugated diene-based polymer using a high molecular compound.
본 발명의 일 실시예에 따른 상기 제조방법은 1) 탄화수소 용매 중에서, 유기 알칼리금속 화합물 존재 하에서 공액디엔계 단량체 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 적어도 일 말단에 알칼리 금속이 결합된 활성 중합체를 제조하는 단계(단계 1); 2) 상기 활성 중합체를 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물과 반응시켜 제1 변성 중합체를 얻는 단계(단계 2); 및 3) 상기 제1 변성 중합체를 실란계 화합물과 반응시키는 단계(단계 3)를 포함하는 변성 공액디엔계 중합체의 제조방법을 포함하는 것을 특징으로 한다.The production method according to an embodiment of the present invention 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).
[화학식 1][Formula 1]
Figure PCTKR2016015106-appb-I000012
Figure PCTKR2016015106-appb-I000012
상기 화학식 1에서, In Chemical Formula 1,
X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
m은 1 내지 50이고,m is 1 to 50,
n은 0 내지 50이고, n is from 0 to 50,
o는 1 내지 50이고,o is from 1 to 50,
p는 1 내지 70이고,p is 1 to 70,
A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
구체적인, 상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 전술한 바와 같다. Specifically, the polymer compound including the structural unit represented by Chemical Formula 1 is as described above.
본 발명의 일 실시예에 따른 변성 공액디엔계 중합체의 제조방법은 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물을 활성 중합체와 반응시킨 후, 연속적으로 실란계 화합물과 반응시키는 단계를 포함함으로써, 변성 공액디엔계 중합체 내에 공액디엔계 중합체, 예를 들어 스티렌-부타디엔 공중합체 사슬과 결합하지 않은 실란기를 포함할 수 있으므로, 일반 변성 공액디엔계 중합체에 비해 실리카와의 친화력을 더욱 향상시킬 수 있다.Method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention 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.
구체적으로 살펴보면, 상기 단계 1은 적어도 일 말단에 알칼리 금속이 결합된 활성 중합체를 제조하기 위한 단계로, 탄화수소 용매 중에서 유기 알칼리금속 화합물 존재 하 공액디엔계 단량체 또는 방향족 비닐계 단량체와 공액디엔계 단량체를 중합함으로써 수행할 수 있다. Specifically, 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. By polymerization.
상기 단계 1의 중합은 단량체로서 공액디엔계 단량체 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 함께 사용하는 것일 수 있다. 즉, 본 발명의 일 실시예에 따른 상기 제조방법을 통해 제조된 중합체는 공액디엔계 단량체 유래의 중합체 또는 방향족 비닐계 단량체와 공액디엔계 단량체 유래의 공중합체일 수 있다. 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.
이때, 상기 공중합체는 랜덤 공중합체일 수 있다.In this case, the copolymer may be a random copolymer.
여기에서, 상기 "랜덤 공중합체(random copolymer)"는 공중합체를 이루는 구성 단위가 무질서하게 배열된 것을 나타내는 것일 수 있다. Here, the "random copolymer" may indicate that the structural units constituting the copolymer are randomly arranged.
상기 공액디엔계 단량체는 특별히 제한되는 것은 아니나, 예컨대 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 피페릴렌, 3-부틸-1,3-옥타디엔, 이소프렌 및 2-페닐-1,3-부타디엔으로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다. 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.
상기 방향족 비닐계 단량체는 특별히 제한되는 것은 아니나, 예컨대 스티렌, α-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌, 4-프로필스티렌, 1-비닐나프탈렌, 4-사이클로헥실스티렌, 4-(p-메틸페닐)스티렌 및 1-비닐-5-헥실나프탈렌으로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다.The aromatic vinyl monomer is not particularly limited, but for example, styrene, α-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.
상기 변성 공액디엔계 중합체가 공액디엔계 단량체 및 방향족 비닐계 단량체유래의 공중합체인 경우, 상기 공액디엔계 단량체는 최종적으로 제조된 변성 공액디엔계 중합체 내 상기 공액디엔계 단량체 유래 단위가 60 중량% 이상, 구체적으로는 60 중량% 내지 90 중량%, 더 구체적으로는 60 중량% 내지 85 중량%로 포함되는 양으로 사용하는 것일 수 있다. When the modified conjugated diene-based polymer is a copolymer derived from a conjugated diene-based monomer and an aromatic vinyl-based monomer, 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. For example, it may be used in an amount of 60 wt% to 90 wt%, more specifically 60 wt% to 85 wt%.
상기 탄화수소 용매는 특별히 제한되는 것은 아니나 예컨대 n-펜탄, n-헥산, n-헵탄, 이소옥탄, 사이클로 헥산, 톨루엔, 벤젠 및 크실렌으로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다. 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.
상기 유기 알칼리금속 화합물은 단량체 총 100 g을 기준으로 0.01 mmol 내지 10 mmol로 사용하는 것일 수 있다. 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.
상기 유기 알칼리금속 화합물은 특별히 제한되는 것은 아니나, 예컨대 메틸리튬, 에틸리튬, 프로필리튬, n-부틸리튬, s-부틸리튬, t-부틸리튬, 헥실리튬, n-데실리튬, t-옥틸리튬, 페닐리튬, 1-나프틸리튬, n-에이코실리튬, 4-부틸페닐리튬, 4-톨릴리튬, 사이클로헥실리튬, 3,5-디-n-헵틸사이클로헥실리튬, 4-사이클로펜틸리튬, 나프틸나트륨, 나프틸칼륨, 리튬 알콕사이드, 나트륨 알콕사이드, 칼륨 알콕사이드, 리튬 술포네이트, 나트륨 술포네이트, 칼륨 술포네이트, 리튬 아미드, 나트륨 아미드, 칼륨아미드, 리튬 이소프로필아미드로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다.  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 isopropylamide Can be.
상기 단계 1의 중합은 필요에 따라 극성 첨가제를 더 첨가하여 수행하는 것일 수 있으며, 상기 극성 첨가제는 단량체 총 100 중량부에 대하여 0.001 중량부 내지 10 중량부로 첨가하는 것일 수 있다. 구체적으로는, 단량체 총 100 중량부에 대하여 0.001 중량부 내지 1 중량부, 더욱 구체적으로는 0.005 중량부 내지 0.1 중량부로 첨가하는 것일 수 있다. 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.
상기 극성 첨가제는 테트라하이드로퓨란, 디테트라하이드로퓨릴프로판, 디에틸에테르, 시클로아말에테르, 디프로필에테르, 에틸렌디메틸에테르, 에틸렌디메틸에테르, 디에틸글리콜, 디메틸에테르, 3차 부톡시에톡시에탄, 비스(3-디메틸아미노에틸)에테르, (디메틸아미노에틸)에틸에테르, 트리메틸아민, 트리에틸아민, 트리프로필아민 및 테트라메틸에틸렌디아민으로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다. 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.
본 발명의 일 실시예에 따른 제조방법은 상기의 극성 첨가제를 사용함으로써 공액디엔계 단량체 및 방향족 비닐계 단량체를 공중합시키는 경우 이들의 반응속도 차이를 보완해줌으로써 랜덤 공중합체를 용이하게 형성할 수 있도록 유도할 수 있다. In the manufacturing method according to an embodiment of the present invention, when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, the reaction rate can be easily compensated for by forming a random copolymer. Can be induced.
상기 단계 1의 중합은 단열중합을 통해 수행하거나, 등온중합을 통해 수행하는 것일 수 있다. The polymerization of step 1 may be carried out through adiabatic polymerization, or isothermal polymerization.
여기에서, 단열중합은 유기 알칼리금속 화합물을 투입한 이후 임의로 열을 가하지 않고 자체 반응열로 중합시키는 단계를 포함하는 중합방법을 나타내는 것이고, 상기 등온중합은 상기 유기 알칼리금속 화합물을 투입한 이후 임의로 열을 가하거나 열을 뺏어 중합물의 온도를 일정하게 유지하는 중합방법을 나타내는 것이다.Here, 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.
상기 중합은 -20℃ 내지 200℃의 온도범위에서 수행하는 것일 수 있으며, 구체적으로는 0℃ 내지 150℃, 더욱 구체적으로는 10℃ 내지 120℃의 온도범위에서 수행하는 것일 수 있다.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.
상기 단계 2는 제1 변성 중합체를 제조하기 위하여, 상기 활성 중합체와 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물과 반응시키는 단계이다. 이때, 제조된 제1 변성 중합체는 공액디엔계 중합체 사슬 일 말단에 상기 화학식 1로표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기가 결합되어 있는 것일 수 있다. 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. In this case, 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.
상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 유기 알칼리금속 화합물 1 몰 대비 0.1 몰 내지 10 몰이 되는 비율로 사용하는 것일 수 있다.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.
본 발명의 일 실시예에 따른 상기 단계 2의 반응은 중합체에 관능기를 도입시키기 위한 변성 반응으로, 상기 반응은 10℃ 내지 120℃의 온도범위에서 10분 내지 5시간 동안 수행하는 것일 수 있다.The reaction of step 2 according to an embodiment of the present invention 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 ℃ to 120 ℃.
본 발명의 일 실시예에 따른 제조방법은 상기 단계 2 이후 필요에 따라 용매 및 미반응 단량체 회수 및 건조 중 1 이상의 단계를 더 포함할 수 있다.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.
한편, 본 발명의 일 실시예에 따른 상기 단계 3의 반응은 상기 단계 2에서 얻은 제1 변성 중합체와 실란계 화합을 반응시킴으로써, 실리카 화합물과의 친화력을 극대화시킬 수 있다. On the other hand, the reaction of step 3 according to an embodiment of the present invention can maximize the affinity with the silica compound by reacting the silane-based compound with the first modified polymer obtained in step 2.
구체적으로 상기 단계 3의 반응에서, 실란계 화합물은 제1 변성 중합체 내에서 공액디엔계 중합체 사슬과 결합하지 않고, 중합체 내의 할로겐 원소와 결합함으로써, 중합체 내에 중합체 사슬과 결합하지 않은 실란기를 포함할 수 있으므로, 일반 변성 공액디엔계 중합체에 비해 실리카와의 친화력이 향상될 수 있다.Specifically, in the reaction of Step 3, 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.
상기 단계 3에서 반응은 10℃ 내지 120℃의 온도범위에서 10분 내지 5시간 동안 수행하는 것일 수 있다. 본 발명의 변성 공액디엔계 중합체의 제조방법은 일례로 하나 또는 둘 이상의 반응기를 포함하는 연속식 중합 방법일 수 있다.In step 3, the reaction may be performed for 10 minutes to 5 hours in a temperature range of 10 ℃ to 120 ℃. 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.
상기 실란계 화합물은 비닐클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필디에톡시실란, 3-글리시독시프로필트리에톡시실란, p-스티릴트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-아크릴옥시프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸부틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 3-클로로프로필트리메톡시실란, 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라설파이드, 및 3-이소시아네이토프로필트리에톡시실란　중에서 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다.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- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylpart Liden) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (tri Ethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane, and any one or a mixture of two or more thereof.
또한, 상기 실란계 화합물은 상기 고분자 화합물 1 몰 대비 0.001 몰 내지 10 몰, 구체적으로는 상기 고분자 화합물 1 몰 대비 0.001 몰 내지 5 몰, 더욱 구체적으로는 0.005 몰 내지 1몰이 되는 비율로 사용하는 것일 수 있다.In addition, 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.
한편, 본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체의 제조방법은 하기 반응식 1에 나타낸 바와 같은 단계를 통하여 수행되는 것일 수 있다. On the other hand, the modified conjugated diene-based polymer manufacturing method according to an embodiment of the present invention may be performed through the steps as shown in Scheme 1.
[반응식 1]Scheme 1
Figure PCTKR2016015106-appb-I000013
Figure PCTKR2016015106-appb-I000013
상기 반응식 1에서, SBR은 스티렌-부타디엔 공중합체 사슬을 나타내는 것이고, m, n, o, o1, o2 및 p는 전술한 바와 같다. In Scheme 1, SBR represents a styrene-butadiene copolymer chain, and m, n, o, o 1 , o 2 and p are as described above.
상기 반응식 1에 나타난 바와 같이, 본 발명의 일 실시예에 따른 상기 제조방법은 스티렌-부타디엔 공중합체를 제조한 후 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물(반응식 1에서 1)과 반응시켜 2로 표시되는 구성단위를 포함하는 화합물(반응식 1에서 2)을 제조하고, 여기에 실란계 화합물(예컨대, 3-아미노프로필트리메톡시실란)과 반응시킴으로써 3으로 표시되는 변성 공액디엔계 중합체(반응식 1에서 3)를 제조하는 것일 수 있다.As shown in Scheme 1, 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.
더 나아가, 본 발명은 상기의 변성 공액디엔계 중합체를 포함하는 고무 조성물을 제공한다.Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
본 발명의 일 실시예에 따른 상기 고무 조성물은 변성 공액디엔계 중합체를 10 중량% 이상, 구체적으로는 10 중량% 내지 100 중량%, 더욱 구체적으로는 20 중량% 내지 90 중량%로 포함하는 것일 수 있다. 만약, 상기 변성 공액디엔계 중합체의 함량이 10 중량% 미만인 경우 결과적으로 상기 고무 조성물을 이용하여 제조된 성형품, 예컨대 타이어의 내마모성 및 내균열성 등의 개선효과가 미미할 수 있다.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.
또한, 상기 고무 조성물은 상기 변성 공액디엔계 중합체 외에 필요에 따라 다른 고무 성분을 더 포함할 수 있으며, 이때 상기 고무 성분은 고무 조성물 총 중량에 대하여 90 중량% 이하의 함량으로 포함될 수 있다. 구체적으로는 상기 변성 공액디엔계 중합체 100 중량부에 대하여 1 중량부 내지 90 중량부로 포함되는 것일 수 있다. In addition, 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. Specifically, 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.
상기 고무 성분은 천연고무 또는 합성고무일 수 있으며, 예컨대 상기 고무 성분은 시스-1,4-폴리이소프렌을 포함하는 천연고무(NR); 상기 일반적인 천연고무를 변성 또는 정제한, 에폭시화 천연고무(ENR), 탈단백 천연고무(DPNR), 수소화 천연고무 등의 변성 천연고무; 스티렌-부타디엔 공중합체(SBR), 폴리부타디엔(BR), 폴리이소프렌(IR), 부틸고무(IIR), 에틸렌-프로필렌 공중합체, 폴리이소부틸렌-코-이소프렌, 네오프렌, 폴리(에틸렌-코-프로필렌), 폴리(스티렌-코-부타디엔), 폴리(스티렌-코-이소프렌), 폴리(스티렌-코-이소프렌-코-부타디엔), 폴리(이소프렌-코-부타디엔), 폴리(에틸렌-코-프로필렌-코-디엔), 폴리설파이드 고무, 아크릴 고무, 우레탄 고무, 실리콘 고무, 에피클로로히드린 고무, 부틸 고무, 할로겐화 부틸 고무 등과 같은 합성고무일 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. 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), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more thereof may be used. have.
또한, 상기 고무 조성물은 변성 공액디엔계 중합체 100 중량부에 대하여 0.1 중량부 내지 200 중량부의 충진제를 포함하는 것일 수 있으며, 상기 충진제는 실리카계 충진제, 카본블랙계 충진제 또는 이들 조합인 것일 수 있다.In addition, 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.
한편, 상기 충전제로서 실리카계 충진제가 사용될 경우 보강성 및 저발열성 개선을 위해 실란 커플링제가 함께 사용될 수 있다. Meanwhile, when the silica-based filler is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.
상기 실란 커플링제로는 구체적으로 비스(3-트리에톡시실릴프로필)테트라술피드, 비스(3-트리에톡시실릴프로필)트리술피드, 비스(3-트리에톡시실릴프로필)디술피드, 비스(2-트리에톡시실릴에틸)테트라술피드, 비스(3-트리메톡시실릴프로필)테트라술피드, 비스(2-트리메톡시실릴에틸)테트라술피드, 3-머캅토프로필트리메톡시실란, 3-머캅토프로필트리에톡시실란, 2-머캅토에틸트리메톡시실란, 2-머캅토에틸트리에톡시실란, 3-트리메톡시실릴프로필-N,N-디메틸티오카르바모일테트라술피드, 3-트리에톡시실릴프로필-N,N-디메틸티오카르바모일테트라술피드, 2-트리에톡시실릴에틸-N,N-디메틸티오카르바모일테트라술피드, 3-트리메톡시실릴프로필벤조티아졸릴테트라술피드, 3-트리에톡시실릴프로필벤졸릴테트라술피드, 3-트리에톡시실릴프로필메타크릴레이트모노술피드, 3-트리메톡시실릴프로필메타크릴레이트모노술피드, 비스(3-디에톡시메틸실릴프로필)테트라술피드, 3-머캅토프로필디메톡시메틸실란, 디메톡시메틸실릴프로필-N,N-디메틸티오카르바모일테트라술피드 또는 디메톡시메틸실릴프로필벤조티아졸릴테트라술피드 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. 보다 구체적으로는 보강성 개선 효과를 고려할 때 상기 실란커플링제는 비스(3-트리에톡시실릴프로필)폴리술피드 또는 3-트리메톡시실릴프로필벤조티아질테트라술피드일 수 있다. Specific examples of the silane coupling agent 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-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.
또, 본 발명에 따른 일 실시예에 따른 상기 고무 조성물에 있어서는, 고무 성분으로서 활성 부위에 실리카계 충전제와의 친화성이 높은 관능기가 도입된 변성 공액디엔계 중합체가 사용되고 있기 때문에, 실란 커플링제의 배합량은 통상의 경우보다 저감될 수 있다. 구체적으로, 상기 실란 커플링제는 실리카계 충전제 100 중량부에 대하여 1 중량부 내지 20 중량부로 사용될 수 있다. 상기한 범위로 사용될 때, 커플링제로서의 효과가 충분히 발휘되면서도 고무 성분의 겔화를 방지할 수 있다. 보다 구체적으로는 상기 실란 커플링제는 실리카 100 중량부에 대하여 5 중량부 내지 15 중량부로 사용될 수 있다. In the rubber composition according to one embodiment of the present invention, 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. Specifically, 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.
또, 본 발명에 따른 일 실시예에 따른 고무 조성물은 황 가교성일 수 있으며, 이에 따라 가황제를 더 포함할 수 있다.In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.
상기 가황제는 구체적으로 황분말일 수 있으며, 고무 성분 100 중량부에 대하여 0.1 중량부 내지 10 중량부로 포함될 수 있다. 상기 함량범위로 포함될 때, 가황 고무 조성물의 필요한 탄성률 및 강도를 확보할 수 있으며, 동시에 저연비성을 얻을 수 있다. 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.
또, 본 발명에 따른 일 실시예에 따른 고무 조성물은 상기한 성분들 외에, 통상 고무 공업계에서 사용되는 각종 첨가제, 구체적으로는 가황 촉진제, 공정유, 가소제, 노화 방지제, 스코치 방지제, 아연화(zinc white), 스테아르산, 열경화성 수지, 또는 열가소성 수지 등을 더 포함할 수 있다.In addition, 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.
상기 가황 촉진제는 특별히 한정되는 것은 아니며, 구체적으로는 M(2-머캅토벤조티아졸), DM(디벤조티아질디술피드), CZ(N-시클로헥실-2-벤조티아질술펜아미드) 등의 티아졸계 화합물, 혹은 DPG(디페닐구아니딘) 등의 구아니딘계 화합물이 사용될 수 있다. 상기 가황촉진제는 고무 성분 100 중량부에 대하여 0.1 중량부 내지 5 중량부로 포함될 수 있다.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.
또, 상기 공정유는 고무 조성물내 연화제로서 작용하는 것으로, 구체적으로는 파라핀계, 나프텐계, 또는 방향족계 화합물일 수 있으며, 보다 구체적으로는 인장 강도 및 내마모성을 고려할 때 방향족계 공정유가, 히스테리시스 손실 및 저온 특성을 고려할 때 나프텐계 또는 파라핀계 공정유가 사용될 수 있다. 상기 공정유는 고무 성분 100 중량부에 대하여 100 중량부 이하의 함량으로 포함될 수 있으며, 상기 함량으로 포함될 때, 가황 고무의 인장 강도, 저발열성(저연비성)의 저하를 방지할 수 있다.In addition, 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.
또, 상기 노화방지제로는 구체적으로 N-이소프로필-N'-페닐-p-페닐렌디아민, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민, 6-에톡시-2,2,4-트리메틸-1,2-디히드로퀴놀린, 또는 디페닐아민과 아세톤의 고온 축합물 등을 들 수 있다. 상기 노화방지제는 고무 성분 100 중량부에 대하여 0.1 중량부 내지 6 중량부로 사용될 수 있다.In addition, as 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.
본 발명의 일 실시예에 따른 고무 조성물은 상기 배합 처방에 의해 밴버리 믹서, 롤, 인터널 믹서 등의 혼련기를 사용하여 혼련함으로써 수득될 수 있으며, 또 성형 가공 후 가황 공정에 의해 저발열성이며 내마모성이 우수한 고무 조성물이 수득될 수 있다.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.
이에 따라 상기 고무 조성물은 타이어 트레드, 언더 트레드, 사이드 월, 카카스 코팅 고무, 벨트 코팅 고무, 비드 필러, 췌이퍼, 또는 비드 코팅 고무 등의 타이어의 각 부재나, 방진고무, 벨트 컨베이어, 호스 등의 각종 공업용 고무 제품의 제조에 유용할 수 있다.Accordingly, 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.
아울러, 본 발명은 상기 고무 조성물을 이용하여 제조된 타이어를 제공한다. In addition, the present invention provides a tire manufactured using the rubber composition.
상기 타이어는 타이어 또는 타이어 트레드를 포함하는 것일 수 있다.The tire may include a tire or a tire tread.
이하, 실시예 및 실험예를 통하여 본 발명을 더 구체적으로 설명한다. 그러나, 하기 실시예 및 실험예는 본 발명을 예시하기 위한 것으로 이들만으로 본 발명의 범위가 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are provided to illustrate the present invention, but the scope of the present invention is not limited only to them.
제조예 1Preparation Example 1
온도조절용 자켓, 용매 응축장치 및 교반장치를 갖추고 있는 5 L 반응기에4-(클로로메틸)스티렌(CMSt) 60.1 g(0.39 mol), 스티렌(SM) 164.1 g(1.58 mol), 2-메톡시에틸아크릴레이트(MEA) 174.2 g(1.34 mol) 및 N,N-디메틸아미노메틸스티렌(DMAMS) 101.6 g (0.63 mol)과 테트라하이드로퓨란(THF) 2 kg을 투입하고, 65℃로 승온 후 5분간 교반시켰다. 이후, 500 ml 비커에 2,2'-아조비스이소부티로니트릴(AIBN) 33.6 g(0.2 mol)을 168.0 g의 테트라하이드로퓨란에 녹인 후 상기 반응기에 주입하고, 65℃에서 12시간 동안 교반하면서 반응시켜 하기 화학식 (i)로 표시되는 구성단위를 포함하는 고분자 화합물인 변성제 A를 제조하였다.60.1 g (0.39 mol) of 4- (chloromethyl) styrene (CMSt), 164.1 g (1.58 mol) of styrene (SM), 2-methoxyethyl in a 5 L reactor with temperature control jacket, solvent condenser and agitator 174.2 g (1.34 mol) of acrylate (MEA), 101.6 g (0.63 mol) of N, N-dimethylaminomethylstyrene (DMAMS) and 2 kg of tetrahydrofuran (THF) were added thereto, and the mixture was heated to 65 ° C and stirred for 5 minutes. I was. Then, 33.6 g (0.2 mol) of 2,2'-azobisisobutyronitrile (AIBN) was dissolved in 168.0 g of tetrahydrofuran in a 500 ml beaker, and then injected into the reactor, and stirred at 65 ° C. for 12 hours. The reaction was carried out to prepare a denaturant A which is a high molecular compound comprising a structural unit represented by the following formula (i).
Figure PCTKR2016015106-appb-I000014
(i)
Figure PCTKR2016015106-appb-I000014
(i)
상기 화학식 (i)에서 m은 10, n은 40, o는 34 및 p는 16이다.In Formula (i), m is 10, n is 40, o is 34 and p is 16.
제조예 2Preparation Example 2
온도조절용 자켓, 용매 응축장치 및 교반장치를 갖추고 있는 5 L 반응기에4-(클로로메틸)스티렌(CMSt) 88.0 g(0.58 mol), 스티렌(SM) 140.2 g(1.35 mol), 2-메톡시에틸아크릴레이트(MEA) 160.2 g(1.23 mol) 및 N,N-디메틸아미노메틸스티렌(DMAMS) 111.6 g (0.69 mol)과 테트라하이드로퓨란(THF) 2 kg을 투입하고, 65℃로 승온 후 5분간 교반시켰다. 이후, 500 ml 비커에 아조비스이소부티로니트릴(AIBN) 35.1 g(0.21 mol)을 168.0 g의 테트라하이드로퓨란에 녹인 후 상기 반응기에 주입하고, 65℃에서 12시간 동안 교반하면서 반응시켜 상기 화학식 (i)로 표시되는 구성단위를 포함하되, m은 15, n은 35, o는 32 및 p는 18인 고분자 화합물인 변성제 B를 제조하였다.88.0 g (0.58 mol) of 4- (chloromethyl) styrene (CMSt), 140.2 g (1.35 mol) of styrene (SM), 2-methoxyethyl in a 5 L reactor with temperature control jacket, solvent condenser and agitator 160.2 g (1.23 mol) of acrylate (MEA), 111.6 g (0.69 mol) of N, N-dimethylaminomethylstyrene (DMAMS) and 2 kg of tetrahydrofuran (THF) were added thereto, and the mixture was heated to 65 ° C. and stirred for 5 minutes. I was. Thereafter, 35.1 g (0.21 mol) of azobisisobutyronitrile (AIBN) was dissolved in 168.0 g of tetrahydrofuran in a 500 ml beaker, injected into the reactor, and reacted with stirring at 65 ° C. for 12 hours. 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.
제조예 3Preparation Example 3
온도조절용 자켓, 용매 응축장치 및 교반장치를 갖추고 있는 5 L 반응기에4-(클로로메틸)스티렌(CMSt) 46.5 g(0.30 mol), 스티렌(SM) 135.0 g(1.30 mol), 2-메톡시에틸아크릴레이트(MEA) 158.7 g(1.22 mol) 및 N,N-디메틸아미노메틸스티렌(DMAMS) 159.8 g (0.99 mol)과 테트라하이드로퓨란(THF) 2 kg을 투입하고, 65℃로 승온 후 5분간 교반시켰다. 이후, 500 ml 비커에 아조비스이소부티로니트릴(AIBN) 34.8 g(0.21 mol)을 168.0 g의 테트라하이드로퓨란에 녹인 후 상기 반응기에 주입하고, 65℃에서 12시간 동안 교반하면서 반응시켜 상기 화학식 (i)로 표시되는 구성단위를 포함하되, m은 8, n은 34, o는 32 및 p는 26인 고분자 화합물인 변성제 C를 제조하였다.46.5 g (0.30 mol) of 4- (chloromethyl) styrene (CMSt), 135.0 g (1.30 mol) of styrene (SM), 2-methoxyethyl in a 5 L reactor with temperature control jacket, solvent condenser and agitator 158.7 g (1.22 mol) of acrylate (MEA) and 159.8 g (0.99 mol) of N, N-dimethylaminomethylstyrene (DMAMS) and 2 kg of tetrahydrofuran (THF) were added thereto, and the mixture was heated to 65 ° C. and stirred for 5 minutes. I was. Then, 34.8 g (0.21 mol) of azobisisobutyronitrile (AIBN) was dissolved in 168.0 g of tetrahydrofuran in a 500 ml beaker, and then injected into the reactor, and reacted with stirring at 65 ° C. for 12 hours to give the above formula ( 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.
제조예 4Preparation Example 4
온도조절용 자켓, 용매 응축장치 및 교반장치를 갖추고 있는 5 L 반응기에 2-(클로로에틸)아크릴레이트(CEA) 34.9 g(0.23 mol), 스티렌(SM) 134.8 g(1.29 mol), 2-메톡시에틸아크릴레이트(MEA) 158.5 g(1.22 mol) 및 N,N-디메틸아미노메틸스티렌(DMAMS) 171.8 g (1.07 mol)과 테트라하이드로퓨란(THF) 2 kg을 투입하고, 65℃로 승온 후 5분간 교반시켰다. 이후, 500 ml 비커에 아조비스이소부티로니트릴(AIBN) 32.6 g(0.2 mol)을 168.0 g의 테트라하이드로퓨란에 녹인 후 상기 반응기에 주입하고, 65℃에서 12시간 동안 교반하면서 반응시켜 하기 화학식 (ii)로 표시되는 구성단위를 포함하는 고분자 화합물인 변성제 D를 제조하였다.34.9 g (0.23 mol) of 2- (chloroethyl) acrylate (CEA), 134.8 g (1.29 mol) of styrene (SM) in 2-liter reactor with temperature control jacket, solvent condenser and agitator 158.5 g (1.22 mol) of ethyl acrylate (MEA) and 171.8 g (1.07 mol) of N, N-dimethylaminomethylstyrene (DMAMS) and 2 kg of tetrahydrofuran (THF) were added thereto, and the temperature was raised to 65 ° C. for 5 minutes. Stirred. Thereafter, 32.6 g (0.2 mol) of azobisisobutyronitrile (AIBN) was dissolved in 168.0 g of tetrahydrofuran in a 500 ml beaker and then injected into the reactor, and reacted with stirring at 65 ° C. for 12 hours. A denaturant D, which is a polymer compound containing the structural unit represented by ii), was prepared.
Figure PCTKR2016015106-appb-I000015
(ii)
Figure PCTKR2016015106-appb-I000015
(ii)
상기 화학식 (ii)에서 m은 6, n은 34, o는 32 및 p는 28이다.In formula (ii), m is 6, n is 34, o is 32 and p is 28.
상기 제조예 1 내지 4에서 제조된 각각의 고분자 화합물인 변성제 A 내지 변성제 D는 분자량 분석을 통하여 합성되었음을 확인하였으며, 그 결과를 하기 표 1에 나타내었다. It was confirmed that the denaturant A to the denaturant D, which is each of the polymer compounds prepared in Preparation Examples 1 to 4, were synthesized through molecular weight analysis, and the results are shown in Table 1 below.
구체적으로, 분자량 분석은 40℃ 조건하에서 GPC 분석으로 측정하였다. 이때 컬럼(Column)은 Polymer Laboratories사의 PLgel Olexis 컬럼 두 자루와 PLgel mixed-C 컬럼 한 자루를 조합하였고, 새로 교체한 컬럼은 모두 mixed bed 타입의 컬럼을 사용하였다. 또한, 분자량 계산시 GPC 기준 물질(Standard material)로서 PS(Polystyrene)를 사용하였다.Specifically, 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. In addition, PS (Polystyrene) was used as the GPC standard material when calculating the molecular weight.
구분division 사용 단량체Used monomer 조성(몰비)Composition (molar ratio) 수평균분자량(g/mol)Number average molecular weight (g / mol) 분자량 분포Molecular weight distribution
변성제 ADenaturant A CMSt/SM/MEA/DMAMSCMSt / SM / MEA / DMAMS 10/40/34/1610/40/34/16 66006600 1.81.8
변성제 BDenaturant B CMSt/SM/MEA/DMAMSCMSt / SM / MEA / DMAMS 15/35/32/1815/35/32/18 64006400 2.22.2
변성제 CDenaturant C CMSt/SM/MEA/DMAMSCMSt / SM / MEA / DMAMS 8/34/32/268/34/32/26 70007000 2.12.1
변성제 DDenaturant D CEA/SM/ODMA/DMAMSCEA / SM / ODMA / DMAMS 6/34/32/286/34/32/28 63006300 1.91.9
실시예 1Example 1
10 L 오토클레이크 반응기에 스티렌 250 g, 1,3-부타디엔 750 g 및 시클로헥산 7 kg, 극성첨가제로 디테트라하이드로퓨릴프로판 0.8 g을 넣은 후 반응기 내부온도를 70℃로 승온하였다. 반응기 내부 온도가 60℃에 도달했을 때, n-부틸리튬 1.53 wt% 노말헥산 용액 0.5 g을 반응기에 투입하여 단열승온 반응을 진행시켰다. 단열승온 반응이 끝나고 40여분 경과 후 중합용액 20 g을 분취하여 이소프로필알콜 100 g에 첨가하고 침전시켜 변성 전 중합체의 특성을 확인하는데 사용하였다. 이후, 상기 제조예 1에서 제조한 변성제 A 32.8 g을 테트라하이드로퓨란 200 g에 녹여서 반응기에 투입하고, 30분간 반응을 진행시키고, 20 g을 분취하여 이소프로필알콜 100 g에 첨가하고 침전시켜 1차 변성 중합체의 특성을 확인하는데 사용하였다. 이후, 3-아미노프로필트리메톡시실란 5.88 g을 10 g의 시클로헥산에 희석하여 투입하고 80℃에서 1시간 동안 추가 반응시켰다. 이소프로필알코올을 이용하여 반응을 정지시키고, 산화방지제인 BHT(부틸레이티드하이드록시톨루엔)가 헥산에 0.3 wt% 녹아있는 용액 45 ml를 첨가하였다. 그 결과 얻어진 중합물을 스팀으로 가열된 온수에 넣고 교반하여 용매를 제거한 다음, 롤 건조하여 잔량의 용매와 물을 제저하여, 변성 스티렌-부타디엔 공중합체를 제조하였다.250 g of styrene, 750 g of 1,3-butadiene, 7 kg of cyclohexane, and 0.8 g of ditetrahydrofurylpropane as a polar additive were added to a 10 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. When the internal temperature of the reactor reached 60 ° C, 0.5 g of n-butyllithium 1.53 wt% normal hexane solution was added to the reactor to proceed with adiabatic heating. After 40 minutes after the adiabatic heating reaction was completed, 20 g of the polymerization solution was aliquoted, added to 100 g of isopropyl alcohol, and precipitated. Thereafter, 32.8 g of the denatured agent A prepared in Preparation Example 1 was dissolved in 200 g of tetrahydrofuran, added to a reactor, the reaction was performed for 30 minutes, 20 g was added to 100 g of isopropyl alcohol, and precipitated. It was used to confirm the properties of the modified polymer. Thereafter, 5.88 g of 3-aminopropyltrimethoxysilane was diluted with 10 g of cyclohexane and further reacted at 80 ° C. for 1 hour. 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. 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.
실시예 2Example 2
변성제 A 대신에 제조예 2에서 제조한 변성제 B 32.8 g을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 변성 스티렌-부타디엔 공중합체를 제조하였다.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.
실시예 3Example 3
변성제 A 대신에 제조예 3에서 제조한 변성제 C 32.8 g을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 변성 스티렌-부타디엔 공중합체를 제조하였다.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.
실시예 4Example 4
변성제 A 대신에 제조예 4에서 제조한 변성체 D 32.8 g을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 변성 스티렌-부타디엔 공중합체를 제조하였다.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.
비교예 1Comparative Example 1
10 L 오토클레이크 반응기에 스티렌 250 g, 1,3-부타디엔 750 g 및 시클로헥산 7 kg, 극성첨가제로 디테트라하이드로퓨릴프로판 0.8 g을 넣은 후 반응기 내부온도를 70℃로 승온하였다. 반응기 내부 온도가 60℃에 도달했을 때, n-부틸리튬 1.53 wt% 노말헥산 용액 0.5 g을 반응기에 투입하여 단열승온 반응을 진행시켰다. 단열승온 반응이 끝나고 40여분 경과 후 중합용액 20 g을 분취하여 이소프로필알콜 100 g에 첨가하고 침전시켜 변성 전 중합체의 특성을 확인하는데 사용하였다. 이후, 상기 제조예 1에서 제조한 변성제 A 32.8 g을 테트라하이드로퓨란 200 g에 녹여서 반응기에 투입하고, 30분간 반응을 진행시시켰다. 이소프로필알코올을 이용하여 반응을 정지시키고, 산화방지제인 BHT(부틸레이티드하이드록시톨루엔)가 헥산에 0.3 wt% 녹아있는 용액 45 ml를 첨가하였다. 그 결과 얻어진 중합물을 스팀으로 가열된 온수에 넣고 교반하여 용매를 제거한 다음, 롤 건조하여 잔량의 용매와 물을 제저하여, 변성 스티렌-부타디엔 공중합체를 제조하였다.250 g of styrene, 750 g of 1,3-butadiene, 7 kg of cyclohexane, and 0.8 g of ditetrahydrofurylpropane as a polar additive were added to a 10 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. When the internal temperature of the reactor reached 60 ° C, 0.5 g of n-butyllithium 1.53 wt% normal hexane solution was added to the reactor to proceed with adiabatic heating. After 40 minutes after the adiabatic heating reaction was completed, 20 g of the polymerization solution was aliquoted, added to 100 g of isopropyl alcohol, and precipitated. Thereafter, 32.8 g of the modifying agent A prepared in Preparation Example 1 was dissolved in 200 g of tetrahydrofuran, and charged into a reactor, and the reaction was performed for 30 minutes. 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. 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.
비교예 2Comparative Example 2
변성제 A 대신에 커플링제로서 테트라클로로실란 10 wt% 노말헥산 용액 2.8 g을 사용한 것을 제외하고는 상기 비교예 1과 동일한 방법을 통하여 스티렌-부타디엔 공중합체를 제조하였다. 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.
비교예 3Comparative Example 3
변성제 A 대신에 3-(N,N-디메틸아미노)프로필 트리메톡시실란(3-(N,N-dimethylamino)propyl trimethoxysilane) 10 wt% 용액 11.3 g을 사용한 것을 제외하고는 실시예 1과 동일한 방법을 통하여 변성 스티렌-부타디엔 공중합체를 제조하였다. 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.
실험예 1Experimental Example 1
상기 실시예 1 내지 실시예 4 및 비교예 1 내지 비교예 3에서 제조된 각 공중합체에 대하여 각각 공중합체 내 스티렌 유래단위 및 비닐 함량, 중량평균분자량(Mw), 수평균분자량(Mn), 최대피크 분자량(Mp), 분자량 분포(MWD, Mw/Mn), 무니점도(MV) 및 규소(Si) 함량을 각각 측정하였다. 결과를 하기 표 2에 나타내었다. For each copolymer prepared in Examples 1 to 4 and Comparative Examples 1 to 3, the styrene-derived unit and vinyl content, weight average molecular weight (Mw), number average molecular weight (Mn), and maximum in the copolymer, respectively Peak molecular weight (Mp), molecular weight distribution (MWD, Mw / Mn), Mooney viscosity (MV) and silicon (Si) content were measured, respectively. The results are shown in Table 2 below.
1) 스티렌 유래단위 및 비닐 함량 분석1) Styrene derived unit and vinyl content analysis
각 공중합체 내 스티렌 유래단위(SM) 및 비닐 함량은 NMR을 이용하여 측정하였다. Styrene derived units (SM) and vinyl content in each copolymer were measured using NMR.
2) 분자량 분석2) Molecular Weight Analysis
40℃ 조건하에서 GPC 분석을 통하여 중량평균 분자량(Mw, g/mol), 수평균 분자량(Mn, g/mol) 및 최대피크 분자량(Mp, g/mol)을 측정하였으며, 분자량 분포(Mw/Mn)는 측정된 중량평균 분자량과 수평균 분자량의 비율로 계산하고, 커플링 수(Mp1/Mp2)는 변성 후 최대피크 분자량(Mp1)과 변성 전 최대피크 분자량(Mp2)를 각각 측정한 후 나눈 값으로 얻었다. 이때 컬럼(Column)은 Polymer Laboratories사의 PLgel Olexis 컬럼 두 자루와 PLgel mixed-C 컬럼 한 자루를 조합하였고, 새로 교체한 컬럼은 모두 mixed bed 타입의 컬럼을 사용하였다. 또한, 분자량 계산시 GPC 기준 물질(Standard material)로서 PS(Polystyrene)를 사용하였다. 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. Got as. 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. In addition, PS (Polystyrene) was used as the GPC standard material when calculating the molecular weight.
3) 무니점도 분석3) Mooney viscosity analysis
각 공중합체의 무니점도(MV, (ML1+4, @100℃))는 MV-2000(Alpha Technologies 社)를 이용하여 Rotor Speed 2±0.02 rpm, Large Rotor를 사용하여 측정하였으며, 이때 사용된 시료는 실온(23±3℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 다이 캐비티 내부에 채워 놓고 Platen을 작동시켜 100℃에서 1분간 예열한 후 4분 동안 측정하였다.Mooney viscosity of each copolymer (MV, (ML1 + 4, @ 100 ℃)) 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 ℃) for 30 minutes or more, 27 ± 3 g was collected, filled into the die cavity, platen was operated, preheated at 100 ℃ for 1 minute, and measured for 4 minutes.
4) 규소(Si) 함량 분석4) Si content analysis
각 공중합체의 규소 함량은 ICP-OES Optima8 300 DV(Perkin Elmer 社)를 이용하여 측정하였다. The silicon content of each copolymer was measured using ICP-OES Optima8 300 DV (Perkin Elmer).
구분division 스티렌(wt%)Styrene (wt%) 비닐(wt%)Vinyl (wt%) GPCGPC 무니점도(MV)Mooney viscosity (MV) Si(ppm)Si (ppm)
Mw(g/mol, X104)Mw (g / mol, X10 4 ) Mn(g/mol, X104)Mn (g / mol, X10 4 ) Mw/MnMw / Mn 커플링 수Coupling Number
실시예 1Example 1 2424 4646 5454 3434 1.61.6 2.42.4 7070 523523
실시예 2Example 2 2525 4747 5454 3232 1.71.7 2.62.6 6969 762762
실시예 3Example 3 2525 4646 6161 3434 1.81.8 2.52.5 7474 369369
실시예 4Example 4 2525 4646 5151 3232 1.61.6 2.22.2 6464 283283
비교예 1Comparative Example 1 2424 4646 5656 3535 1.61.6 2.42.4 7171 <10<10
비교예 2Comparative Example 2 2424 4545 5959 3737 1.61.6 2.42.4 7474 5656
비교예 3Comparative Example 3 2424 4646 4545 3232 1.41.4 1.81.8 5656 145145
상기 표 2에서 커플링 수는 중합체 사슬이 변성제에 의하여 커플링되거나 변성되었음을 나타내는 것으로 그 수가 클수록 커플링 또는 변성이 더 높은 비율로 이루어졌음을 나타내는 것이다. 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.
상기 표 2에 나타난 바와 같이, 본 발명의 일 실시예에 따른 실시예 1 내지 실시예 4의 커플링 수는 모두 2를 초과하였으며 이를 통하여 변성이 이루어졌음을 확인하였다.As shown in Table 2, the number of couplings of Examples 1 to 4 according to an embodiment of the present invention all exceeded 2, and it was confirmed that the modification was made.
실험예 2Experimental Example 2
상기 실시예 1 내지 4 및 비교예 1 내지 3의 각 공중합체를 포함하는 고무 조성물 및 이로부터 제조된 성형품의 물성을 비교분석하였으며, 그 결과를 하기 표 3에 나타내었다. The physical properties of the rubber composition and the molded article prepared from each of the copolymers of Examples 1 to 4 and Comparative Examples 1 to 3 were compared, and the results are shown in Table 3 below.
1) 고무 조성물의 제조1) Preparation of Rubber Composition
각 고무 조성물은 제1단 혼련, 제2단 혼련 및 제3단 혼련과정을 거쳐 제조하였다. 이때, 변성 공액디엔계 공중합체를 제외한 물질의 사용량은 변성 공액디엔계 공중합체 100 중량부를 기준으로 하여 나타낸 것이다. 제1단 혼련에서는 온도제어장치를 부속한 반바리믹서를 사용하여 80 rpm 조건으로 상기 각 공중합체 100 중량부, 실리카 70 중량부, 실란 커플링제로서 비스(3-트리에톡시실릴프로필)테트라술피드 11.02 중량부, 공정오일(process oil, TDAE) 33.75 중량부, 노화방지제(TMDQ) 2.0 중량부, 산화방지제 2.0 중량부, 산화아연(ZnO) 3.0 중량부, 스테아린산(stearic acid) 2.0 중량부 및 왁스 1.0 중량부를 배합하여 혼련하였다. 이때, 혼련기의 온도를 제어하고 140℃~150℃의 배출온도에서 1차 배합물을 얻었다. 제2단 혼련에서는 상기 1차 배합물을 실온까지 냉각한 후 혼련기에 고무 촉진제(CZ) 1.75 중량부, 황분말 1.5 중량부, 가황촉진제 2.0 중량부를 첨가하고 60℃ 이하의 온도에서 믹싱하여 2차 배합물을 얻었다. 이 후 제3단 혼련에서 2차 배합물을 성형하고, 180℃에서 t90+10분 동안 가황프레스로 가황하여 각 가황고무를 제조하였다. 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. In the first stage kneading, 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. 11.02 parts by weight of feed, 33.75 parts by weight of process oil (TDAE), 2.0 parts by weight of antioxidant (TMDQ), 2.0 parts by weight of antioxidant, 3.0 parts by weight of zinc oxide (ZnO), 2.0 parts by weight of stearic acid, and 1.0 weight part of waxes were blended and kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at the discharge temperature of 140 ° C to 150 ° C. In 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.
2) 무니점도2) Mooney viscosity
무니점도(MV, (ML1+4, @100℃))는 ALPHA Technologies 社의 MV-2000을 이용하여 Rotor Speed 2±0.02 rpm, Large Rotor를 사용하여 1차 배합물(1단 혼련) 및 2차 배합물(2단 혼련)에 대하여 각각 측정하였으며, 이때 사용된 시료는 실온(23±3℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 다이 캐비티 내부에 채워놓고 Platen을 작동시켜 100℃에서 1분 동안 예열한 후 4분 동안 측정하였다. 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 ℃) for more than 30 minutes, and then collected 27 ± 3 g, filled in the die cavity, and platen operated at 100 ℃. Preheat for 1 minute and then measure for 4 minutes.
3) 페이니 효과(Payne effect, △G') 분석3) Payne effect (△ G ') analysis
ALPHA Technologies 社의 RPA 2000을 이용하여 각 가황고무 7 g을 60℃에서 1 Hz의 속도로 0.04% 내지 40%에서 strain swip으로 측정하고 최소값과 최대값의 차이로 나타내었다. 이때, 페이니 효과가 작을수록 실리카와 같은 충전제의 분산성이 우수함을 나타낸다. 7 g of each vulcanized rubber was measured by strain swip at 0.04% to 40% at a rate of 1 Hz at 60 ° C. using RPA 2000 of ALPHA Technologies, Inc. and expressed as the difference between the minimum and maximum values. In this case, the smaller the Penny effect, the better the dispersibility of the filler such as silica.
4) 인장특성4) Tensile Characteristics
인장특성은 ASTM 412의 인장시험법에 준하여 각 시험편(두께 25 mm, 길이 80 mm)을 제조하고 상기 시험편의 절단시의 인장강도 및 300% 신장시의 인장응력(300% 모듈러스)를 측정하였다. 구체적으로, 인장특성은 Universal Test Machine 4204(Instron 社) 인장 시험기를 이용하여 실온에서 50 cm/min의 속도로 측정하여 인장강도 및 300% 신장시의 인장응력 값을 얻었다. 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.
5) 점탄성 특성5) viscoelastic properties
점탄성 특성은 동적 기계 분석기(TA 社)를 이용하여 비틀림 모드로 주파수 10 Hz, 각 측정온도(0℃~60℃)에서 변형을 변화시켜 Tan δ를 측정하였다. 이때, 저온 0℃에서의 Tan δ가 높을수록 제동성이 우수하고, 고온 60℃ Tan δ가 낮을수록 히스테리시스 손실이 적고, 저구름 저항성(연비성)이 우수함을 나타낸다. 결과값은 비교예 3의 공중합체를 포함하는 고무 조성물의 측정값을 100 기준으로 하여 Index 수치로 나타내었으며, Index 수치가 증가할수록 우수함을 의미한다. 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.). In this case, the higher the Tan δ at low temperature 0 ° C., the better the braking performance. The lower the high temperature 60 ° C. Tan δ, 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.
6) 내마모성6) wear resistance
DIN 마모 측정기를 이용하여 측정하였다. 결과값은 비교예 3의 공중합체를 포함하는 고무 조성물의 측정값을 100 기준으로 하여 Index 수치로 비교하였으며, Index 수치가 증가할수록 우수함을 의미한다.It was measured using a DIN wear meter. The result was compared with the index value on the basis of the measured value of the rubber composition containing the copolymer of Comparative Example 3 based on 100, meaning that the higher the index value increases.
구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
무니점도 (MV)Mooney viscosity (MV) 1단 혼련1 st kneading 7171 6868 6464 6262 6969 6666 6262
2단 혼련Two-stage kneading 5858 5757 5656 5454 6262 6161 5454
페이니 효과(△G')Payney Effect (△ G ') 0.440.44 0.430.43 0.420.42 0.450.45 0.560.56 0.580.58 0.460.46
인장특성Tensile Properties 300% 모듈러스(Index)300% Modulus (Index) 104104 108108 104104 102102 9898 9797 100100
인장강도(Index)Tensile Strength (Index) 103103 103103 101101 101101 9797 9696 100100
점탄성 특성Viscoelastic properties Tan δ at 0℃Tan δ at 0 ℃ 104104 106106 103103 104104 9494 9292 100100
Tan δ at 60℃Tan δ at 60 ℃ 108108 110110 106106 105105 9393 8282 100100
내마모성(Index)Wear Resistance (Index) 103103 104104 9999 101101 100100 9797 100100
상기 표 3의 결과에서, 본 발명에 따른 고분자 화합물을 변성제로 이용하여 제조된 실시예 1 내지 실시예 4의 변성 스티렌-부타디엔 공중합체를 포함하는 고무 조성물이 종래의 일반적인 변성제를 사용하여 제조된 비교예 3의 변성 스티렌-부타디엔 공중합체를 포함하는 고무 조성물 대비 300% 모듈러스 및 인장 강도가 동등 수준 이상을 나타내면서, 젖은 노면에 대한 제동성(0℃ Tan δ)이 3%~6% 수준으로 상승하고 저구름 저항성(60℃ Tan δ)이 5%~10%로 크게 향상되었음을 확인하였다. In the results of Table 3, a rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 to 4 prepared using the polymer compound according to the present invention as a modifier was prepared using a conventional general modifier When the rubber composition comprising the modified styrene-butadiene copolymer of Example 3 exhibited an equivalent level of 300% modulus and tensile strength or more, braking property (0 ° C. Tan δ) on a wet road surface rose to a level of 3% to 6%. Low cloud resistance (60 ℃ Tan δ) was confirmed that greatly improved to 5% ~ 10%.
한편, 본 발명의 일 실시예에 따른 실시예 1 내지 실시예 4의 변성 스티렌-부타디엔 공중합체를 포함하는 고무 조성물이 미변성된 비교예 1 및 비교예 2의 공액디엔계 중합체를 포함하는 고무 조성물 대비 젖은 노면에 대한 저항 특성, 연비 특성, 기계적 물성 등 모든 측면에서 향상된 성능을 보임을 확인하였다.On the other hand, 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.
또한, 본 발명의 일 실시예에 따른 실시예 1 내지 실시예 4의 변성 스티렌-부타디엔 공중합체를 포함하는 고무 조성물로부터 제조된 시편이 비교예 1 내지 비교예 3의 미변성 또는 변성 스티렌-부타디엔 공중합체를 포함하는 고무 조성물로부터 제조된 시편 대비 페이니 효과에 있어 크게 감소된 수치를 나타내었으며, 이를 통하여 상기 실시예 1 내지 실시예 4의 변성 스티렌-부타디엔 공중합체를 포함하는 고무 조성물 내 실리카의 분산성이 비교예 1 내지 비교예 3의 고무 조성물 내 실리카의 분산성보다 우수한 것임을 알 수 있다. 이는, 본 발명의 일 실시예에 따른 실시예 1 내지 실시예 4의 변성 스티렌-부타디엔 공중합체가 실리가, 즉 충전제와의 친화성이 우수함을 나타내는 것이다.In addition, 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 In comparison with the specimen prepared from the rubber composition including the copolymer showed a significantly reduced numerical value, through which 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.

Claims (20)

  1. 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물:A polymer compound comprising a structural unit represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2016015106-appb-I000016
    Figure PCTKR2016015106-appb-I000016
    상기 화학식 1에서, In Chemical Formula 1,
    X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
    m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
    m은 1 내지 50이고,m is 1 to 50,
    n은 0 내지 50이고, n is from 0 to 50,
    o는 1 내지 50이고,o is from 1 to 50,
    p는 1 내지 70이고,p is 1 to 70,
    A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1에서, In Chemical Formula 1,
    X1은 할로겐으로 치환된 탄소수 1 내지 10의 알킬기, 에스테르기 또는 알킬아릴기인 것인 고분자 화합물. X 1 is a polymer compound having an alkyl group, ester group or alkylaryl group having 1 to 10 carbon atoms substituted by halogen.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1에서, In Chemical Formula 1,
    X2는 탄소수 1 내지 3의 알킬기 또는 탄소수 3 내지 10의 사이클로알킬기로치환되거나 비치환된 탄소수 6 내지 10의 아릴기인 것인 고분자 화합물. X 2 is a high molecular compound having 6 to 10 carbon atoms or an unsubstituted aryl group having 1 to 3 carbon atoms or an alkyl group having 3 to 10 carbon atoms.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1에서, In Chemical Formula 1,
    X3는 하기 화학식 2로 표시되는 것인 고분자 화합물:X 3 is a polymer compound represented by Formula 2 below:
    [화학식 2][Formula 2]
    Figure PCTKR2016015106-appb-I000017
    Figure PCTKR2016015106-appb-I000017
    상기 화학식 2에서,In Chemical Formula 2,
    R1은 에스테르기이고,R 1 is an ester group,
    R2는 탄소수 1 내지 20의 알킬기이며, R 2 is an alkyl group having 1 to 20 carbon atoms,
    a는 0 내지 10의 정수이다. a is an integer of 0-10.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1에서,In Chemical Formula 1,
    X4는 하기 화학식 3으로 표시되는 것인 고분자 화합물:X 4 is a polymer compound represented by Formula 3 below:
    [화학식 3][Formula 3]
    Figure PCTKR2016015106-appb-I000018
    Figure PCTKR2016015106-appb-I000018
    상기 화학식 3에서,In Chemical Formula 3,
    R3은 탄소수 1 내지 6의 알킬렌기, 에스테르기 또는 탄소수 6 내지 10의 아릴렌기이고,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,
    R4 및 R5는 서로 독립적으로 탄소수 1 내지 10의 알킬기이거나, 서로 연결되어 탄소수 3 내지 10의 고리 구조를 형성하는 것이며,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,
    b는 1 내지 8의 정수이다.b is an integer of 1-8.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 구성단위를 포함하는 것인 고분자 화합물:A polymer compound comprising a structural unit represented by Formula 1 includes a structural unit represented by Formula 4 or Formula 5 below:
    [화학식 4][Formula 4]
    Figure PCTKR2016015106-appb-I000019
    Figure PCTKR2016015106-appb-I000019
    [화학식 5][Formula 5]
    Figure PCTKR2016015106-appb-I000020
    Figure PCTKR2016015106-appb-I000020
    상기 화학식 4 및 화학식 5에서,In Chemical Formulas 4 and 5,
    m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
    m은 1 내지 50이고,m is 1 to 50,
    n은 0 내지 50이고, n is from 0 to 50,
    o는 1 내지 50이고,o is from 1 to 50,
    p는 1 내지 70이다.p is 1 to 70.
  7. 청구항 1에 있어서,The method according to claim 1,
    상기 고분자 화합물은 공액디엔계 중합체용 변성제인 것인 고분자 화합물.The high molecular compound is a high molecular compound for the conjugated diene polymer.
  8. 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물 유래 작용기를 포함하는 변성 공액디엔계 중합체:Modified conjugated diene-based polymer comprising a functional group derived from a high molecular compound comprising a structural unit represented by the formula (1):
    [화학식 1] [Formula 1]
    Figure PCTKR2016015106-appb-I000021
    Figure PCTKR2016015106-appb-I000021
    상기 화학식 1에서, In Chemical Formula 1,
    X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
    m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
    m은 1 내지 50이고,m is 1 to 50,
    n은 0 내지 50이고, n is from 0 to 50,
    o는 1 내지 50이고,o is from 1 to 50,
    p는 1 내지 70이고,p is 1 to 70,
    A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  9. 청구항 8에 있어서,The method according to claim 8,
    상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 구성단위를 포함하는 것인 변성 공액디엔계 중합체:Modified conjugated diene-based polymer comprising a structural unit represented by the formula (4) or formula (5) comprising a structural unit represented by the formula (1):
    [화학식 4][Formula 4]
    Figure PCTKR2016015106-appb-I000022
    Figure PCTKR2016015106-appb-I000022
    [화학식 5][Formula 5]
    Figure PCTKR2016015106-appb-I000023
    Figure PCTKR2016015106-appb-I000023
    상기 화학식 4 및 화학식 5에서,In Chemical Formulas 4 and 5,
    m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
    m은 1 내지 50이고,m is 1 to 50,
    n은 0 내지 50이고, n is from 0 to 50,
    o는 1 내지 50이고,o is from 1 to 50,
    p는 1 내지 70이다.p is 1 to 70.
  10. 청구항 8에 있어서,The method according to claim 8,
    상기 중합체는 중합체 전체 중량 대비 100 ppm 내지 10,000 ppm의 실란기를 포함하는 것인 변성 공액디엔계 중합체.Wherein said polymer comprises from 100 ppm to 10,000 ppm of silane groups relative to the total weight of the polymer.
  11. 청구항 8에 있어서,The method according to claim 8,
    상기 중합체는 방향족 비닐계 단량체 유래 단위를 40 중량% 이하로 포함하는 것인 변성 공액디엔계 중합체.The polymer is a modified conjugated diene-based polymer comprising an aromatic vinyl monomer-derived unit at 40% by weight or less.
  12. 청구항 8에 있어서,The method according to claim 8,
    상기 중합체는 수평균 분자량이 10,000 g/mol 내지 1,000,000 g/mol인 것인 변성 공액디엔계 중합체.The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 10,000 g / mol to 1,000,000 g / mol.
  13. 1) 탄화수소 용매 중에서, 유기 알칼리금속 화합물 존재 하에서 공액디엔계방향족 단량체 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 적어도 일 말단에 알칼리 금속이 결합된 활성 중합체를 제조하는 단계; 1) polymerizing a conjugated diene aromatic 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 thereof;
    2) 상기 활성 중합체를 하기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물과 반응시켜 제1 변성 중합체를 얻는 단계; 및2) 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) 상기 제1 변성 중합체를 실란계 화합물과 반응시키는 단계를 포함하는 청구항 8에 기재된 변성 공액디엔계 중합체의 제조방법:3) A method for producing the modified conjugated diene polymer according to claim 8 comprising the step of reacting the first modified polymer with a silane compound:
    [화학식 1][Formula 1]
    Figure PCTKR2016015106-appb-I000024
    Figure PCTKR2016015106-appb-I000024
    상기 화학식 1에서, In Chemical Formula 1,
    X1, X2, X3 및 X4는 서로 독립적으로 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 또는 비치환된 탄소수 1 내지 10의 알킬기, 아민기, 에스테르기, 니트릴기, 벤조페논기, 아크릴기, 비닐기, 스티렌기, 스티렌아크릴기 또는 아릴기를 포함하는 화합물 유래 치환기이고, 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 A substituent derived from a compound containing 1 to 10 alkyl groups, amine groups, ester groups, nitrile groups, benzophenone groups, acrylic groups, vinyl groups, styrene groups, styreneacryl groups, or aryl groups,
    m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
    m은 1 내지 50이고,m is 1 to 50,
    n은 0 내지 50이고, n is from 0 to 50,
    o는 1 내지 50이고,o is from 1 to 50,
    p는 1 내지 70이고,p is 1 to 70,
    A1 내지 A4는 서로 독립적으로 수소원자 또는 탄소수 1 내지 3의 알킬기이다.A 1 to A 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  14. 청구항 13에 있어서,The method according to claim 13,
    상기 화학식 1로 표시되는 구성단위를 포함하는 고분자 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 구성단위를 포함하는 것인 변성 공액디엔계 중합체의 제조방법:Method for producing a modified conjugated diene-based polymer that comprises a structural unit represented by the formula (4) or formula (5) comprising a structural unit represented by the formula (1):
    [화학식 4][Formula 4]
    Figure PCTKR2016015106-appb-I000025
    Figure PCTKR2016015106-appb-I000025
    [화학식 5][Formula 5]
    Figure PCTKR2016015106-appb-I000026
    Figure PCTKR2016015106-appb-I000026
    상기 화학식 4 및 화학식 5에서,In Chemical Formulas 4 and 5,
    m, n, o 및 p는 각 반복 단위체의 몰비율을 나타내는 것으로 m+n+o+p는 100이고,m, n, o and p represent the molar ratio of each repeating unit, m + n + o + p is 100,
    m은 1 내지 50이고,m is 1 to 50,
    n은 0 내지 50이고, n is from 0 to 50,
    o는 1 내지 50이고,o is from 1 to 50,
    p는 1 내지 70이다.p is 1 to 70.
  15. 청구항 13에 있어서,The method according to claim 13,
    상기 유기 알칼리금속 화합물은 단량체 총 100 g을 기준으로 0.01 mmol 내지 10 mmol로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.The organoalkali metal compound is a method for producing a modified conjugated diene-based polymer that is used in 0.01 mmol to 10 mmol based on a total of 100 g of the monomer.
  16. 청구항 13에 있어서,The method according to claim 13,
    상기 단계 1)의 중합은 극성 첨가제를 더 첨가하여 수행하는 것인 변성 공액디엔계 중합체의 제조방법. The polymerization of step 1) is a method for producing a modified conjugated diene-based polymer further by adding a polar additive.
  17. 청구항 16에 있어서,The method according to claim 16,
    상기 극성 첨가제는 단량체 총 100 중량부 대비 0.001 중량부 내지 10 중량부로 첨가하는 것인 변성 공액디엔계 중합체의 제조방법.The polar additive is a method for producing a modified conjugated diene-based polymer is added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer.
  18. 청구항 13에 있어서,The method according to claim 13,
    상기 고분자 화합물은 유기 알칼리금속 화합물 1 몰 대비 0.1 몰 내지 10 몰이 되는 비율로 사용하는 것인 변성 공액디엔계 중합체의 제조방법. The polymer compound is a method for producing a modified conjugated diene-based polymer that is used in a ratio of 0.1 to 10 moles relative to 1 mole of the organic alkali metal compound.
  19. 청구항 13에 있어서,The method according to claim 13,
    상기 실란계 화합물은 고분자 화합물 1몰 대비 0.001 몰 내지 10 몰이 되는 비율로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.The silane-based compound is a method for producing a modified conjugated diene-based polymer that is used in a ratio of 0.001 to 10 moles relative to 1 mole of the polymer compound.
  20. 청구항 13에 있어서,The method according to claim 13,
    상기 실란계 화합물은 비닐클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필디에톡시실란, 3-글리시독시프로필트리에톡시실란, p-스티릴트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-아크릴옥시프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸부틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 3-클로로프로필트리메톡시실란, 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라설파이드, 및 3-이소시아네이토프로필트리에톡시실란　중에서 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것인 변성 공액디엔계 중합체의 제조방법.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- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylpart Liden) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (tri A method for producing a modified conjugated diene-based polymer, which is any one selected from ethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane, or a mixture of two or more thereof.
PCT/KR2016/015106 2015-12-24 2016-12-22 Polymer compound, method for preparing modified conjugated diene-based polymer by using same, and modified conjugated diene-based polymer WO2017111499A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114174350A (en) * 2019-08-06 2022-03-11 旭化成株式会社 Conjugated diene polymer, branching agent, method for producing conjugated diene polymer, oil-extended conjugated diene polymer, rubber composition, and tire
US11560442B2 (en) 2017-04-10 2023-01-24 Synthomer Adhesive Technologies Llc Functionalized resin having a polar linker

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57171796A (en) * 1981-04-13 1982-10-22 Deitsuku Haakiyuresu Kk Anti-slip method of paper
US4397994A (en) 1980-09-20 1983-08-09 Japan Synthetic Rubber Co., Ltd. High vinyl polybutadiene or styrene-butadiene copolymer
JP2009086345A (en) * 2007-09-28 2009-04-23 Fujifilm Corp Lithographic printing plate precursor
JP2010070615A (en) * 2008-09-17 2010-04-02 Univ Of Tsukuba Crosslinked polymer composition for surface treatment of support
KR20150134035A (en) * 2014-05-21 2015-12-01 주식회사 엘지화학 Modified Conjugated Diene Polymer And Method For Preparing The Same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397994A (en) 1980-09-20 1983-08-09 Japan Synthetic Rubber Co., Ltd. High vinyl polybutadiene or styrene-butadiene copolymer
JPS57171796A (en) * 1981-04-13 1982-10-22 Deitsuku Haakiyuresu Kk Anti-slip method of paper
JP2009086345A (en) * 2007-09-28 2009-04-23 Fujifilm Corp Lithographic printing plate precursor
JP2010070615A (en) * 2008-09-17 2010-04-02 Univ Of Tsukuba Crosslinked polymer composition for surface treatment of support
KR20150134035A (en) * 2014-05-21 2015-12-01 주식회사 엘지화학 Modified Conjugated Diene Polymer And Method For Preparing The Same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DUONG, H. T. T. ET AL.: "Organic Nitrate Functional Nanoparticles for the Glutathione -triggered Slow-release of Nitric Oxide", JOURNAL OF POLYMER SCIENCE PART A, POLYMER CHEMISTRY, vol. 52, no. 5, 4 May 2014 (2014-05-04), pages 2099 - 2103, XP055451917 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11560442B2 (en) 2017-04-10 2023-01-24 Synthomer Adhesive Technologies Llc Functionalized resin having a polar linker
US11820843B2 (en) 2017-04-10 2023-11-21 Synthomer Adhesive Technologies Llc Functionalized resin having a polar linker
CN114174350A (en) * 2019-08-06 2022-03-11 旭化成株式会社 Conjugated diene polymer, branching agent, method for producing conjugated diene polymer, oil-extended conjugated diene polymer, rubber composition, and tire
EP4011642A4 (en) * 2019-08-06 2022-10-19 Asahi Kasei Kabushiki Kaisha Conjugated-diene-based polymer, branching agent, method for producing conjugated-diene-based polymer, oil-extended conjugated-diene-based polymer, rubber composition, and tire
CN114174350B (en) * 2019-08-06 2024-04-30 旭化成株式会社 Conjugated diene polymer, process for producing the same, oil-extended conjugated diene polymer, rubber composition, and tire

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