WO2019066279A1 - Polymère diénique conjugué modifié aux deux extrémités et son procédé de production - Google Patents

Polymère diénique conjugué modifié aux deux extrémités et son procédé de production Download PDF

Info

Publication number
WO2019066279A1
WO2019066279A1 PCT/KR2018/010238 KR2018010238W WO2019066279A1 WO 2019066279 A1 WO2019066279 A1 WO 2019066279A1 KR 2018010238 W KR2018010238 W KR 2018010238W WO 2019066279 A1 WO2019066279 A1 WO 2019066279A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
group
independently
formula
conjugated diene
Prior art date
Application number
PCT/KR2018/010238
Other languages
English (en)
Korean (ko)
Inventor
김민수
이수용
최원문
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180081572A external-priority patent/KR102102986B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2019520360A priority Critical patent/JP6714777B2/ja
Priority to EP18859974.0A priority patent/EP3508509B1/fr
Priority to CN201880021507.1A priority patent/CN110475794B/zh
Priority to US16/345,793 priority patent/US11319394B2/en
Publication of WO2019066279A1 publication Critical patent/WO2019066279A1/fr

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F236/14—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 containing elements other than carbon and hydrogen

Definitions

  • the present invention relates to a two-end modified conjugated diene polymer comprising a functional group derived from a modified polymerization initiator and a functional group derived from a modifier and having improved affinity with a filler and improved mechanical properties and viscoelastic properties, and a method for producing the same.
  • Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem of low wet skid resistance.
  • a conjugated diene (co) polymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) is prepared by emulsion polymerization or solution polymerization and is used as a rubber for a tire .
  • the glass transition temperature of the rubber is increased by increasing the vinyl content in the SBR, so that the tire required properties such as running resistance and braking force can be controlled, By adjusting the fuel consumption can be reduced.
  • the filler such as SBR and silica or carbon black
  • a method of modifying the polymerizable active site of the conjugated diene polymer obtained by anionic polymerization using organolithium with a functional group capable of interacting with the filler For example, there has been proposed a method in which the polymerization active terminal of the conjugated diene polymer is modified with a tin compound, an amine group is introduced, or an alkoxysilane derivative is modified.
  • U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the end of a polymer chain obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, which is a monofunctional initiator, is bonded using a binder such as a tin compound .
  • carbon black and silica are used as reinforcing fillers for tire treads.
  • silica is used as a reinforcing filler, low hysteresis loss property and wet skid resistance are improved.
  • silica having a hydrophilic surface compared to carbon black on the hydrophobic surface has a disadvantage that the affinity with the rubber is low and the dispersibility is poor. Therefore, in order to improve the dispersibility or to provide the bond between the silica and the rubber, It is necessary to use a lingering agent.
  • the present invention has been conceived to solve the problems of the prior art described above, and it is an object of the present invention to provide a two-terminal modified conjugated diene having excellent affinity with a filler and having improved mechanical properties and viscoelasticity properties including a functional group derived from a modified polymerization initiator and a functional group derived from a modifier Based polymer.
  • the present invention also provides a process for producing the modified conjugated diene polymer.
  • the present invention provides a modified conjugated diene polymer comprising a functional group derived from a compound represented by the following formula (1) at one end and a functional group derived from a modifier represented by the following formula do:
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms
  • R 2 is a divalent hydrocarbon group of 1 to 20 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of 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 ,
  • R 3 and R 4 are each independently selected from the group consisting of 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 and having 1 to 20 carbon atoms Is a monovalent hydrocarbon group,
  • X is S or O
  • R 5 and R 6 are each independently a monovalent hydrocarbon group of 1 to 30 carbon atoms or , At least one of R < 5 > and R < 6 > is a glycol unit,
  • R 7 is a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 12 is a divalent hydrocarbon group of 1 to 10 carbon atoms
  • j and k are each independently 0 or 1
  • n is an integer of 1 to 10
  • R 5 is a glycol unit, 3-il and i are independently 1 or 2 but not 2, l is 0 or 1,
  • R 6 is a glycol unit, i and l are independently 1 or 2 but not 2, 3-il is 0 or 1,
  • R 5 and R 6 are both glycol units, i is 1 or 2, and l and 3-yl are independently 0 or 1, but not 0 at the same time.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms
  • R 2 is a divalent hydrocarbon group of 1 to 20 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of 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 ,
  • R 3 and R 4 are each independently selected from the group consisting of 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 and having 1 to 20 carbon atoms Is a monovalent hydrocarbon group,
  • X is S or O
  • R 5 and R 6 are each independently a monovalent hydrocarbon group of 1 to 30 carbon atoms or , At least one of R < 5 > and R < 6 > is a glycol unit,
  • R 7 is a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 12 is a divalent hydrocarbon group of 1 to 10 carbon atoms
  • j and k are each independently 0 or 1
  • n is an integer of 1 to 10
  • R 5 is a glycol unit, 3-il and i are independently 1 or 2 but not 2, l is 0 or 1,
  • R 6 is a glycol unit, i and l are independently 1 or 2 but not 2, 3-il is 0 or 1,
  • R 5 and R 6 are both glycol units, i is 1 or 2, and l and 3-yl are independently 0 or 1, but not 0 at the same time.
  • the modified conjugated diene polymer according to the present invention contains a functional group derived from a compound represented by the formula (1) at its one end and a functional group derived from a modifier represented by the formula (2) at the other end thereof, thereby having excellent affinity with a filler such as silica And can be excellent in processability, mechanical properties and viscoelasticity.
  • the production method according to the present invention can easily introduce a functional group derived from a compound represented by the formula (1) at the terminal end of a polymer chain by preparing an active polymer in the presence of a modified polymerization initiator prepared using the compound represented by the formula ,
  • the modifier-derived functional group represented by the general formula (2) can be easily introduced into the other end of the polymer chain by reacting the active polymer with the modifier represented by the general formula (2).
  • the modified conjugated diene polymer can be easily produced.
  • substituted means that the hydrogen of a functional group, an atomic group or a compound is substituted with a specific substituent, and when a hydrogen atom of a functional group, an atomic group or a compound is substituted with a specific substituent, One or more than two substituents may be present depending on the number of hydrogen atoms. When a plurality of substituents are present, the respective substituents may be the same as or different from each other.
  • alkyl group used in the present invention may mean a monovalent aliphatic saturated hydrocarbon and includes linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl, , Tert-butyl, and neo-pentyl.
  • alkyl &quot alkyl "
  • alkylene group used in the present invention may mean a bivalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.
  • cycloalkyl group may mean cyclic saturated hydrocarbon.
  • aryl group used in the present invention means a cyclic aromatic hydrocarbon, and may be a monocyclic aromatic hydrocarbon having one ring formed therein or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto polycyclic aromatic hydrocarbons.
  • derived unit and " derived functional group” used in the present invention may refer to a component, structure, or the substance itself resulting from a substance.
  • monovalent hydrocarbon group used in the present invention refers to a monovalent substituent derived from a hydrocarbon group, and includes, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, And the monovalent atomic group may have a linear or branched structure depending on the structure of the univalent atomic group.
  • divalent hydrocarbon group used in the present invention indicates a divalent substituent derived from a hydrocarbon group, and examples thereof include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, and an arylene group including an unsaturated bond May be a bivalent atomic group having carbon and hydrogen bonded thereto, and the bivalent atomic group may have a linear or branched structure depending on the structure of the bond.
  • the present invention provides a modified conjugated diene polymer having an excellent affinity for a filler, particularly a silica-based filler, to which a functional group is introduced at both ends of the polymer chain.
  • the modified conjugated diene polymer according to one embodiment of the present invention comprises a compound derived from a compound represented by the following formula 1 at one end and a functional group derived from a modifier represented by the following formula 2 at the other end do.
  • R 1 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms
  • R 2 is a divalent hydrocarbon group of 1 to 20 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of 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 ,
  • R 3 and R 4 are each independently selected from the group consisting of 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 and having 1 to 20 carbon atoms Is a monovalent hydrocarbon group,
  • X is S or O
  • R 5 and R 6 are each independently a monovalent hydrocarbon group of 1 to 30 carbon atoms or , At least one of R < 5 > and R < 6 > is a glycol unit,
  • R 7 is a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 12 is a divalent hydrocarbon group of 1 to 10 carbon atoms
  • j and k are each independently 0 or 1
  • n is an integer of 1 to 10
  • R 5 is a glycol unit, 3-il and i are independently 1 or 2 but not 2, l is 0 or 1,
  • R 6 is a glycol unit, i and l are independently 1 or 2 but not 2, 3-il is 0 or 1,
  • R 5 and R 6 are both glycol units, i is 1 or 2, and l and 3-yl are independently 0 or 1, but not 0 at the same time.
  • R 1 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 3 to 12 carbon atoms A cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms.
  • R 2 when R 2 is substituted with a substituent or may have two of the unsubstituted C1 to C20 may hydrocarbon group, a divalent hydrocarbon group having 1 to 20 carbon atoms wherein the R 2 is unsubstituted in the above formula (I) wherein R 2 is An alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group or a propylene group; An arylene group having 6 to 20 carbon atoms such as a phenylene group and the like; Or an arylalkylene group having 7 to 20 carbon atoms as a combinator thereof.
  • R 2 is a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a substituent
  • one or more hydrogen atoms bonded to carbon atoms in the hydrocarbon group may be substituted with a substituent.
  • the substituent may be one or more selected from the group consisting of 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, and specifically includes an alkyl group having 1 to 10 carbon atoms, To 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
  • R 3 and R 4 are optionally substituted with independently a substituent with each other in the can 1
  • the unsubstituted C1 to C20 can be a hydrocarbon group, wherein R 3 and R 4 is to a carbon number of 1 ring carbon atoms Beach each other when a monovalent hydrocarbon group of 20 wherein R 3 and R 4 are selected from the group consisting of an aryl group, and arylalkyl group having 7 to 20 of carbon number of 1 to 20 alkyl group, C 3 -C 20 cycloalkyl group, having 6 to 20 carbon atoms in the Specifically, R 1 may be selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms .
  • R 3 and R 4 are independently a monovalent hydrocarbon group of 1 to 20 carbon atoms substituted with a substituent
  • one or more hydrogen atoms bonded to carbon atoms in the hydrocarbon group may be substituted with a substituent.
  • the substituent may be one or more selected from the group consisting of 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, and specifically includes an alkyl group having 1 to 10 carbon atoms, To 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
  • R 1 in the general formula 1 according to the embodiment of the invention is an aryl group of a hydrogen atom, a C 1 -C 10 alkyl, C 3 -C 12 cycloalkyl group or a group having 6 to 12 carbon atoms of, R 2 has a carbon number And R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X may be S or O .
  • R 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 2 is an alkylene group having 1 to 6 carbon atoms
  • R 3 and R 4 are independently an alkyl group having 1 to 6 carbon atoms
  • X may be O.
  • R 5 and R 6 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms or , And at least one of R 5 and R 6 may be a glycol unit.
  • R 5 is a glycol unit
  • 3-yl and i are independently 1 or 2 but not 2
  • 1 is 0 or 1
  • R 6 is a glycol unit
  • i and l are each independently 1 or 2 is not simultaneously 2
  • 3-il is 0 or 1
  • R 5 and R 6 are both glycol units, i is 1 or 2
  • l and 3-yl are independently 0 or 1,
  • R 11 may be a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • n may be an integer of 1 to 10.
  • R < 5 > and R < 6 > Wherein R 11 may be an alkyl group having 1 to 10 carbon atoms, and n may be an integer of 2 to 8.
  • R 7 may be a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms, and when R 7 is a divalent hydrocarbon group, R 7 may be a divalent hydrocarbon group having 1 to 30 carbon atoms such as a methylene group, An alkylene group having 1 to 20 carbon atoms; An arylene group having 6 to 20 carbon atoms such as a phenylene group and the like; Or an arylalkylene group having 7 to 20 carbon atoms as a combinator thereof. Specifically, R 7 may be an alkylene group having 1 to 10 carbon atoms.
  • R < 8 > To R 10 each independently represent a monovalent hydrocarbon group having 1 to 30 carbon atoms, and specifically, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms
  • Arylalkyl groups of 1 to 10 carbon atoms and more specifically may be independently of each other an alkyl group of 1 to 10 carbon atoms.
  • R 12 may be a divalent hydrocarbon group having 1 to 10 carbon atoms, and specifically may be an alkylene group having 2 to 6 carbon atoms.
  • R < 5 > and R < 6 & , R 7 is an alkylene group having 1 to 10 carbon atoms
  • R 12 represents an alkylene group having 2 to 6 carbon atoms
  • i is an integer of 1 or 2
  • 3-il and 1 are each independently an integer of 0 or 1
  • n may be an integer of 2 to 8.
  • the compound represented by Formula 1 may be a compound represented by Formula 1-1.
  • the modifier represented by Formula 2 is N, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxyhexadecane- Amines such as N, N-bis (3- (diethoxy (methyl) silyl) propyl) -2,5,8,11,14-pentaoxyhexadecane- (2- (2-methoxyethoxy) ethoxy) ethyl) -3- (triethoxysilyl) propane- (Triethoxysilyl) propane-1-amine, N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanone 3- (triethoxysilyl) -N- (3- (triethoxysilyl) propyl) - N - (2- (2- methoxyethoxy) ethyl) Propan-1-amine, N- (2- (2- (2- methoxyethoxy) e
  • the modified conjugated diene polymer according to the present invention may be one prepared by a production method described later and may be a homopolymer of a conjugated diene monomer or a modified polymer of a copolymer of a conjugated diene monomer and an aromatic vinyl monomer have. At this time, the copolymer may be a random copolymer.
  • random copolymer may indicate that the modified constituent units constituting the copolymer are randomly arranged.
  • the modified conjugated diene polymer according to an embodiment of the present invention has a tertiary amine group which is a functional group derived from a compound represented by the formula (1) at one end and a tertiary amine group which is a functional group derived from a denaturant represented by the formula (2)
  • An alkylene glycol group and an alkoxysilane group prevents the hydrogen bonding between the hydroxyl groups present on the surface of the filler, thereby preventing agglomeration between the fillers and improving the dispersibility of the filler.
  • the alkylene glycol group may improve the affinity of the polymer chain with the filler to improve the processability of the polymer.
  • the alkoxysilane group may have a functional group on the surface of the filler, for example, when the filler is silica, And the abrasion resistance and processability of the polymer can be improved.
  • the modified conjugated diene polymer according to one embodiment of the present invention may have excellent affinity with a filler, particularly silica, because it contains a functional group derived from a compound represented by the formula (1) and a functional group derived from a modifier And thus the compounding property with the filler can be excellent, so that the processability of the rubber composition containing the modified conjugated diene polymer can be improved.
  • the molded product produced using the rubber composition such as the tensile strength, abrasion resistance And viscoelastic properties can be improved.
  • the modified conjugated diene polymer may have a number average molecular weight (Mn) of 100,000 g / mol to 1,000,000 g / mol, specifically 400,000 g / mol to 700,000 g / mol.
  • Mn number average molecular weight
  • the modified conjugated diene polymer may have a weight average molecular weight (Mw) of 200,000 g / mol to 1,500,000 g / mol, specifically 500,000 g / mol to 1,200,000 g / mol.
  • Mw weight average molecular weight
  • the modified conjugated diene polymer may have a molecular weight distribution (Mw / Mn) of 1.0 to 3.0. Specifically, the molecular weight distribution may be 1.0 to 2.0.
  • the modified conjugated diene polymer according to an embodiment of the present invention may have a molecular weight distribution range as described above and a weight average molecular weight
  • the average molecular weight and the number average molecular weight may simultaneously satisfy the above-mentioned range of conditions.
  • the modified conjugated diene polymer may have a molecular weight distribution of 3.0 or less, a weight average molecular weight of 200,000 g / mol to 1,500,000 g / mol, and a number average molecular weight of 100,000 g / mol to 1,000,000 g / mol , More specifically polydispersity of 2.0 or less, weight average molecular weight of 500,000 g / mol to 1,200,000 g / mol, and number average molecular weight of 400,000 g / mol to 700,000 g / mol.
  • the weight average molecular weight and the number average molecular weight are respectively polystyrene reduced molecular weights analyzed by gel permeation chromatography (GPC), molecular weight distribution (Mw / Mn) is also called polydispersity, weight average molecular weight (Mw) And the number-average molecular weight (Mn) (Mw / Mn).
  • the modified conjugated diene 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.
  • vinyl content When the vinyl content is in the above range, Can be adjusted to an appropriate range. Therefore, when the tire is applied to a tire, it is excellent in physical properties required for a tire such as a running resistance and a braking force, and also has an effect of reducing fuel consumption.
  • the vinyl content indicates the content of the 1,2-added conjugated diene monomer, not 1,4-added to 100% by weight of the conjugated diene-based polymer composed of the vinyl group-containing monomer or the conjugated diene-based monomer.
  • the modified conjugated diene polymer according to an embodiment of the present invention may be a polymer having high linearity with a value of -S / R (stress / relaxation) at 100 ° C of 0.7 or more.
  • -S / R represents a change in stress due to the reaction of the same amount of strain generated in the material, and is an index indicating the linearity of the polymer.
  • the lower the -S / R value means the lower the linearity of the polymer, and the lower the linearity, the greater the rolling resistance or the rolling resistance when applied to the rubber composition.
  • the degree of branching and the molecular weight distribution of the polymer can be predicted from the above-S / R value. The lower the S / R value, the higher the degree of branching and the broader the molecular weight distribution. As a result, Characteristics are low.
  • the modified conjugated diene polymer according to an embodiment of the present invention has a high-S / R value of 0.7 or more at 100 ⁇ as described above, resistance characteristics and fuel consumption characteristics can be excellent when applied to a rubber composition.
  • the -S / R value of the modified conjugated diene-based polymer may be 0.7 to 1.2.
  • the -S / R value was measured using a Mooney viscometer, for example, a large rotor of Monsanto MV2000E at 100 ° C and a rotor speed of 2 ⁇ 0.02 rpm. Specifically, the polymer was allowed to stand at room temperature (23 ⁇ 5 ° C) for 30 minutes or more, 27 ⁇ 3 g was collected, filled in the die cavity, and the platen was operated to measure the Mooney viscosity while applying the torque. The -S / R value was obtained by measuring the slope of the Mooney viscosity change as the torque was released for one minute.
  • the present invention also provides a process for producing the above-mentioned modified conjugated diene polymer.
  • a method for producing a modified polymerization initiator comprising: (1) preparing a modified polymerization initiator by reacting a compound represented by the following formula (1) with an organic alkali metal compound in a hydrocarbon solvent; Polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of the modified polymerization initiator to produce an active polymer having a functional group derived from the compound represented by the formula (1) at its one end (step 2); And a step of reacting the active polymer with a modifier represented by the following formula (2) (step 3).
  • R 1 to R 4 , R 5 to R 10 , 3-yl, i, l, j and k in the general formulas (1) and (2) are as defined above for the modified conjugated diene polymer.
  • the step 1 is a step for preparing a modified polymerization initiator comprising a compound-derived unit represented by the formula (1), and may be carried out by reacting a compound represented by the formula (1) with an organic alkali metal compound in a hydrocarbon solvent.
  • the compound represented by Formula 1 and the organic alkali metal compound may be reacted at a molar ratio of 1: 0.8-3.
  • the unit derived from the compound represented by the formula (1) and the unit derived from the organic alkali metal compound are easily bonded to each other, .
  • the functional group derived from the compound represented by the general formula (1) can be introduced into the end of the polymer chain while easily forming the active polymer in the step 2 described later.
  • the bond may indicate that the metal component derived from the organic alkali metal compound is ionically bonded with the carbon of the unit derived from the compound represented by the formula (1).
  • the organic alkali metal compound may be, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- Butyl lithium, 4-tolyl lithium, cyclohexyl lithium, 3,5-di-n-heptyl cyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium , At least one selected from the group consisting of lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropyl amide.
  • the organic alkali metal compound may be n-butyllithium.
  • the hydrocarbon solvent is not particularly limited, but may be one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
  • a polar solvent when the compound represented by Formula 1 is reacted with the organic alkali metal compound, a polar solvent may be added as needed.
  • the polar solvent when a polar solvent is added, the polar solvent may be used in an amount of 0.5 to 1.1 equivalents to 1 equivalent of the organic alkali metal compound.
  • the polar solvent is not particularly limited, but may be one or more selected from the group consisting of trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine, and specifically may be tetramethylethylenediamine .
  • step 1 may be carried out at 50 ° C to 70 ° C for 20 minutes to 30 minutes.
  • the step 2 is a step for preparing an active polymer having a functional group derived from a compound represented by the formula (1) introduced at one end thereof.
  • the conjugated diene-based monomer or the aromatic vinyl monomer and the conjugated diene Can be carried out by polymerizing the monomer.
  • conjugated diene monomer examples include, but are not limited to, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, -1,3-butadiene, and the like.
  • the conjugated diene-based monomer has a unit derived from the conjugated diene-based monomer in the finally produced modified conjugated diene-based polymer in an amount of 60% by weight or more, And may be used in an amount of 60 wt% or more and less than 100 wt%, more specifically 60 wt% to 85 wt%.
  • aromatic vinyl monomer examples include, but are not limited to, styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- -Methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.
  • the amount of the aromatic vinyl-based monomer-derived unit in the finally produced modified conjugated diene-based polymer is 40% by weight or less, More preferably from 40% by weight to more than 0% by weight, and more specifically from 15% by weight to 40% by weight.
  • the modified polymerization initiator may be used in an amount of 0.05 part by weight to 0.3 part by weight based on 100 g of the total amount of the monomers.
  • the polymerization of the step 2 may be carried out by adding a polar additive if necessary, and the polar additive may be added in an amount of 0.001 part by weight to 10 parts by weight based on 100 parts by weight of the total amount of the monomers. Specifically, it may be added in an amount of 0.001 part by weight to 1 part by weight, more desirably 0.005 part by weight to 0.2 part by weight, based on 100 parts by weight of the total amount of monomers.
  • the polar additive may be selected from the group consisting of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis Aminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.
  • the random copolymer can be easily formed .
  • the polymerization in the step 2 may be an elevated temperature polymerization, an isothermal polymerization or a constant temperature polymerization (adiabatic polymerization).
  • the constant temperature polymerization represents a polymerization method including a step of polymerizing by self heat of reaction without any heat after initiating the polymerization
  • the above-mentioned elevated temperature polymerization is a polymerization method in which heat is optionally applied after the initiation of the polymerization to increase the temperature
  • the isothermal polymerization is a polymerization method in which heat is applied after heat initiation to increase the heat or heat is taken to keep the temperature of the polymer constant.
  • the polymerization may be carried out at a temperature in the range of -20 to 200 ⁇ , and specifically in a temperature range of 20 to 150 ⁇ , more specifically 30 to 120 ⁇ for 15 minutes to 3 hours . If the polymerization is carried out in the above temperature range, the polymerization reaction can be controlled easily, and the polymerization reaction rate and efficiency can be excellent.
  • Step 3 may be carried out by reacting the active polymer with the modifier represented by Formula 2 as a step for preparing the modified conjugated diene polymer.
  • step 3 may be a denaturation step.
  • the modifier represented by the formula (2) may be used in a ratio of 0.8 mol to 1.5 mol based on 1 mol of the modified polymerization initiator.
  • the modifier is used in such an amount as to give the above range, the modifying reaction with the optimum performance can be performed, and the conjugated diene polymer having a high modification ratio can be obtained.
  • the reaction of step 3 may be a modification reaction for introducing a functional group into the polymer, and the reaction may be carried out at a temperature range of 10 ° C to 120 ° C for 10 minutes to 5 hours.
  • the method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention may be carried out by a continuous polymerization method including batch type (batch type) or one or more kinds of reactors.
  • an ethylene or isopropanol solution or the like may be added to the polymerization reaction system to terminate the polymerization reaction.
  • the modified conjugated diene polymer can be obtained through desolvation treatment or vacuum drying treatment such as steam stripping which lowers the partial pressure of the solvent through supply of water vapor.
  • the reaction product obtained as a result of the above-mentioned denaturation reaction may contain an unmodified active polymer together with the above-mentioned modified conjugated diene polymer.
  • the manufacturing method according to an embodiment of the present invention may further include at least one post-processing step during recovery and drying of solvent and unreacted monomers, if necessary, after step 3, and the post- It may be carried out by adding hot water heated with steam and stirring to remove the solvent, followed by roll drying to remove the remaining solvent and water.
  • the present invention provides a rubber composition comprising the modified conjugated diene polymer and a molded article produced from the rubber composition.
  • the rubber composition according to an embodiment of the present invention contains the modified conjugated diene polymer in an amount of 0.1 to 100% by weight, specifically 10 to 100% by weight, more specifically 20 to 90% by weight May include. If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the abrasion resistance and crack resistance of a molded article produced using the rubber composition, such as a tire, may be insignificant.
  • the rubber composition may further include other rubber components, if necessary, in addition to the modified conjugated diene polymer, wherein the rubber component may be contained in an amount of 90 wt% or less based on the total weight of the rubber composition. Specifically, it may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.
  • the rubber component may be natural rubber or synthetic rubber, for example natural rubber (NR) comprising cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, poly Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber and the like, and any one or a mixture of two or more thereof may be used.
  • NR natural rubber
  • the rubber composition may contain 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer, and the filler may be silica-based, carbon black or a combination thereof. Specifically, the filler may be carbon black.
  • the carbon black filler is not particularly limited, but may have a nitrogen adsorption specific surface area (measured according to N 2 SA, JIS K 6217-2: 2001) of 20 m 2 / g to 250 m 2 / g.
  • the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100 g to 200 cc / 100 g. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m 2 / g, the workability of the rubber composition may deteriorate. If it is less than 20 m 2 / g, the reinforcing performance by carbon black may be insufficient.
  • the workability of the rubber composition may decrease. If the DBP oil absorption is less than 80 cc / 100 g, the reinforcing performance by carbon black may be insufficient.
  • the silica is not particularly limited, but may be, for example, wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica.
  • the silica may be a wet silica having the most remarkable effect of improving the destructive property and the wet grip.
  • the silica has a nitrogen surface area per gram (N 2 SA) of 120 m 2 / g to 180 m 2 / g and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m 2 / / g.
  • N 2 SA nitrogen surface area per gram
  • CTAB cetyl trimethyl ammonium bromide
  • the reinforcing performance by silica may be lowered. If it exceeds 180 m < 2 > / g, If the CTAB adsorption specific surface area of the silica is less than 100 m < 2 > / g, the reinforcing performance by the silica as a filler may be deteriorated. If it exceeds 200 m < 2 > / g, the workability of the rubber composition may deteriorate.
  • silica when used as the filler, a silane coupling agent may be used together to improve the reinforcing property and the low heat build-up.
  • silane coupling agent examples include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxys
  • the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazine tetrasulfide.
  • the amount of the silane coupling agent it can be reduced more than usual.
  • the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight based on 100 parts by weight of the filler.
  • the silane coupling agent may be used in an amount of 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 may further include a vulcanizing agent.
  • the vulcanizing agent may be specifically a sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.
  • the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, such as a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.
  • a vulcanization accelerator such as a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.
  • the vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used.
  • the vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
  • the process oil may be a paraffinic, naphthenic, or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics.
  • the process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.
  • the antioxidant examples include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone.
  • the antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.
  • the rubber composition according to one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.
  • a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.
  • the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, Can be useful for the production of various industrial rubber products.
  • the molded article produced using the rubber composition may be one comprising a tire or tire tread.
  • N, N-dimethyl-2- (4-vinylphenoxy) ethan- 1- amine was obtained as a pale yellow liquid by vacuum distillation.
  • the obtained N, N-dimethyl-2- (4-vinylphenoxy) ethan-1 -amine was confirmed by 1 H nuclear magnetic resonance spectroscopy ( 1 H NMR).
  • N, N-dimethyl-3- (4-vinylphenoxy) propan-1- amine was obtained as a transparent liquid through vacuum distillation.
  • the obtained N, N-dimethyl-2- (4-vinylphenoxy) ethan-1 -amine was confirmed by 1 H nuclear magnetic resonance spectroscopy ( 1 H NMR).
  • the obtained N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine was analyzed by 1H nuclear magnetic resonance spectroscopy (1 H NMR) Respectively.
  • N, N-dimethyl-4-vinyl aniline was obtained by distillation under reduced pressure.
  • the obtained N, N-dimethyl-4-vinyl aniline was confirmed by 1 H nuclear magnetic resonance spectroscopy ( 1 H NMR).
  • a 20 L autoclave reactor was charged with 2 kg of n-hexane, 2.62 g of N, N-dimethyl-2- (4-vinylphenoxy) ethane-1- amine prepared in Preparation Example 1 and 176 g % in n-hexane) and 1.59 g of tetramethylethylenediamine (TMEDA) were charged and reacted at 60 DEG C for 30 minutes to prepare a modified polymerization initiator.
  • TMEDA tetramethylethylenediamine
  • N, N-dimethyl-2- (4-vinylphenoxy) ethane-1-amine prepared in Preparation Example 2 was obtained in the same manner as in Example 1, -Vinylphenoxy) propane-1-amine was added in an amount of 2.82 g, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1.
  • N-dimethyl-2- (4-vinylphenoxy) ethane-1-amine prepared in Production Example 3 was obtained in the same manner as in Example 1, butadiene copolymer was prepared in the same manner as in Example 1, except that 3.02 g of 4-vinylphenoxy) ethyne-1-amine was added.
  • the reaction was stopped using ethanol, and 33 g of a solution in which 30 wt% of Wingstay K, an antioxidant, was dissolved in hexane was added.
  • the resultant polymer was put into hot water heated with steam and stirred to remove the solvent.
  • the solvent was then removed by roll drying to remove the remaining solvent and water to prepare a modified styrene-butadiene copolymer.
  • N-dimethyl-4-vinylpyridine prepared in Comparative Preparation Example 1 was used in place of N, N-dimethyl-2- (4-vinylphenoxy) Modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that 2.04 g of aniline was added.
  • SM styrene derived unit
  • vinyl content in each copolymer were measured by NMR.
  • Each of the polymers was dissolved in tetrahydrofuran (THF) for 30 minutes under the condition of 40 ⁇ ⁇ and loaded on gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • two columns of PLgel Olexis column and one column of PLgel mixed-C column of Polymer Laboratories were used in combination.
  • a column of a mixed bed type was used as a new column, and polystyrene was used as a gel permeation chromatography (GPC) standard material.
  • the Mooney viscosity (MV) was measured at 100 ° C using Rotor Speed 2 ⁇ 0.02 rpm using Monsanto MV2000E with a large rotor. The sample used was allowed to stand at room temperature (23 ⁇ 3 ° C) for more than 30 minutes, and then 27 ⁇ 3 g was sampled and filled in the die cavity. Platen was operated to measure the Mooney viscosity by applying torque.
  • the modified styrene-butadiene copolymer of the example prepared by using the modified polymerization initiator according to one embodiment of the present invention is a copolymer of styrene-butadiene copolymer of Comparative Example 1 prepared by using n-butyllithium as a polymerization initiator (Styrene-derived unit and vinyl content) as compared with the modified styrene-butadiene copolymer.
  • n-butyllithium as a polymerization initiator (Styrene-derived unit and vinyl content) as compared with the modified styrene-butadiene copolymer.
  • the rubber compositions and the rubber specimens were prepared using the modified styrene-butadiene copolymer and the styrene-butadiene copolymer prepared in the above Examples and Comparative Examples, and then their Mooney viscosity, tensile property, viscoelastic property and abrasion resistance were measured by the following methods Respectively. The results are shown in Table 2 below.
  • each rubber specimen was manufactured through a first stage kneading and a second stage kneading process. At this time, the amount of the substance excluding the copolymer is shown based on 100 parts by weight of the copolymer.
  • the Mooney viscosity of each of the secondary blends obtained in the preparation of the rubber specimens was measured and the processability characteristics were compared and analyzed. At this time, the lower the measured value of the Mooney viscosity, the better the workability characteristic.
  • the Mooney viscosity was MV2000E manufactured by Monsanto and the Mooney viscosity (MV) was measured at 100 ° C using Rotor Speed 2 ⁇ 0.02 rpm using a large rotor. The sample used was allowed to stand at room temperature (23 ⁇ 3 ° C) for more than 30 minutes, and then 27 ⁇ 3 g was sampled and filled in the die cavity. Platen was operated to measure the Mooney viscosity by applying torque.
  • Tensile properties of each test piece were measured in accordance with the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece and the tensile stress at 300% elongation (300% modulus) were measured. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester to obtain tensile strength and tensile stress values at 300% elongation.
  • the viscoelastic properties were measured by using a dynamic mechanical analyzer (TA) at a frequency of 10 Hz in a twist mode at various measuring temperatures (0 ° C to 70 ° C) to measure Tan ⁇ .
  • TA dynamic mechanical analyzer
  • the tan ⁇ at 0 ° C shows wet grip and the tan ⁇ at 60 ° C shows the fuel economy.
  • the measured value was represented by indexing the measured value of Comparative Example 1 as 100.
  • the abrasion resistance was measured by using a DIN abrasion tester, a load of 10 N was applied to a rotating drum having abrasion paper attached thereto, each rubber specimen was moved in a direction perpendicular to the rotation direction of the drum, and then the amount of abrasion loss was measured.
  • the rotational speed of the drum was 40 rpm, and the total travel distance of the specimen at the completion of the test was 40 m.
  • the measured value was represented by indexing the measured value of Comparative Example 1 as 100.
  • the rubber specimens prepared using the hosierystylated styrene-butadiene copolymers of Examples 1 to 3 according to one embodiment of the present invention were the same as those of Comparative Examples 1 to 4 Or a modified styrene-butadiene copolymer, it was confirmed that the rubber composition of the present invention had excellent tensile properties and compounding workability as well as excellent viscoelastic properties and abrasion resistance as compared with the rubber specimens prepared using the modified styrene-butadiene copolymer.
  • Examples 1 to 3 exhibited excellent tensile properties and markedly improved viscoelastic properties and abrasion resistance as compared with Comparative Example 1, which is an unmodified styrene-butadiene copolymer.
  • Comparative Example 1 is an unmodified styrene-butadiene copolymer.
  • Mooney viscosity (CMV) It was confirmed that the blending processability was also remarkably excellent.
  • Examples 1 to 3 exhibited excellent tensile and abrasion resistance, and particularly improved viscoelastic properties, as compared with Comparative Example 2 and Comparative Example 3, which are terminal styrene-butadiene copolymers.
  • Example 1 It was also confirmed that the tensile properties and wear resistance of Example 1 were improved compared to Comparative Example 4, which is a styrene-butadiene copolymer of both ends, and Tan ⁇ value at 60 ° C, At this time, the horseshoe-modified styrene-butadiene copolymer of Comparative Example 4 was produced under the same conditions as in Example 1 except that the modifying polymerization initiator was partially different (prepared by using a compound in which X was absent in Formula 1) .

Landscapes

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

Abstract

La présente invention concerne : un polymère diénique conjugué modifié aux deux extrémités, qui comprend un groupe fonctionnel dérivé d'un initiateur de polymérisation modifié et un groupe fonctionnel dérivé d'un modificateur et présente une excellente affinité avec une matière de charge, possédant ainsi des propriétés mécaniques et viscoélastiques améliorées; et un procédé de production de celui-ci.
PCT/KR2018/010238 2017-09-29 2018-09-03 Polymère diénique conjugué modifié aux deux extrémités et son procédé de production WO2019066279A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2019520360A JP6714777B2 (ja) 2017-09-29 2018-09-03 両末端変性共役ジエン系重合体およびその製造方法
EP18859974.0A EP3508509B1 (fr) 2017-09-29 2018-09-03 Polymère diénique conjugué modifié aux deux extrémités et son procédé de production
CN201880021507.1A CN110475794B (zh) 2017-09-29 2018-09-03 两末端改性共轭二烯类聚合物及其制备方法
US16/345,793 US11319394B2 (en) 2017-09-29 2018-09-03 Both terminal-modified conjugated diene-based polymer and method for preparing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170126961 2017-09-29
KR10-2017-0126961 2017-09-29
KR10-2018-0081572 2018-07-13
KR1020180081572A KR102102986B1 (ko) 2017-09-29 2018-07-13 양 말단 변성 공액디엔계 중합체 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2019066279A1 true WO2019066279A1 (fr) 2019-04-04

Family

ID=65903800

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/010238 WO2019066279A1 (fr) 2017-09-29 2018-09-03 Polymère diénique conjugué modifié aux deux extrémités et son procédé de production

Country Status (1)

Country Link
WO (1) WO2019066279A1 (fr)

Citations (7)

* 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
KR20120046721A (ko) * 2009-06-30 2012-05-10 가부시키가이샤 브리지스톤 음이온 중합 개시제 및 방법
KR20140028133A (ko) * 2011-08-26 2014-03-07 아사히 가세이 케미칼즈 가부시키가이샤 변성 공액 디엔계 중합체의 제조 방법, 변성 공액 디엔계 중합체, 변성 공액 디엔계 중합체 조성물, 고무 조성물, 및 타이어
KR20160065733A (ko) * 2014-12-01 2016-06-09 주식회사 엘지화학 아민기를 포함하는 음이온 말단을 갖는 음이온 중합 개시제, 이를 이용한 변성 공역디엔계 공중합체의 제조방법, 및 이에 따라 제조한 변성 공역디엔계 공중합체를 포함하는 고무 조성물
KR20160079323A (ko) * 2014-12-26 2016-07-06 한화토탈 주식회사 변성 공액디엔계 중합체 및 그를 포함하는 조성물
WO2016162482A1 (fr) * 2015-04-10 2016-10-13 Synthos S.A. Initiateurs pour la copolymérisation de monomères diéniques et de monomères aromatiques vinyliques
KR20170075662A (ko) * 2015-12-23 2017-07-03 주식회사 엘지화학 변성 공액디엔계 중합체, 이의 제조방법 및 변성제

Patent Citations (7)

* 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
KR20120046721A (ko) * 2009-06-30 2012-05-10 가부시키가이샤 브리지스톤 음이온 중합 개시제 및 방법
KR20140028133A (ko) * 2011-08-26 2014-03-07 아사히 가세이 케미칼즈 가부시키가이샤 변성 공액 디엔계 중합체의 제조 방법, 변성 공액 디엔계 중합체, 변성 공액 디엔계 중합체 조성물, 고무 조성물, 및 타이어
KR20160065733A (ko) * 2014-12-01 2016-06-09 주식회사 엘지화학 아민기를 포함하는 음이온 말단을 갖는 음이온 중합 개시제, 이를 이용한 변성 공역디엔계 공중합체의 제조방법, 및 이에 따라 제조한 변성 공역디엔계 공중합체를 포함하는 고무 조성물
KR20160079323A (ko) * 2014-12-26 2016-07-06 한화토탈 주식회사 변성 공액디엔계 중합체 및 그를 포함하는 조성물
WO2016162482A1 (fr) * 2015-04-10 2016-10-13 Synthos S.A. Initiateurs pour la copolymérisation de monomères diéniques et de monomères aromatiques vinyliques
KR20170075662A (ko) * 2015-12-23 2017-07-03 주식회사 엘지화학 변성 공액디엔계 중합체, 이의 제조방법 및 변성제

Similar Documents

Publication Publication Date Title
WO2019112260A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2018128288A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc en contenant
WO2017217720A1 (fr) Procédé de préparation d'un polymère à base de diène conjugué modifié, et polymère à base de diène conjugué modifié préparé à l'aide du procédé de préparation
WO2018128285A1 (fr) Procédé de préparation d'un polymère à base de diène conjugué modifié
WO2019216636A1 (fr) Polymère de diène conjugué modifié et composition de caoutchouc comprenant celui-ci
WO2019216645A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2018128290A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2020013638A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc comprenant celui-ci
WO2017191921A1 (fr) Agent de modification et polymère à base de diène conjugué modifié produit à l'aide de celui-ci
WO2018128291A1 (fr) Polymère diène conjugué modifié et composition de caoutchouc le comprenant
WO2017105012A1 (fr) Polymère modifié, procédé pour le produire, et composition de caoutchouc le comprenant
WO2017111487A1 (fr) Polymère à base d'un diène conjugué modifié et procédé de préparation de ce polymère
WO2018105845A1 (fr) Modificateur et polymère à base de diène conjugué modifié, et procédés de préparation associés
WO2017188641A2 (fr) Polymère à base de diène conjugué modifié et procédé de préparation associé
WO2019112262A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2018128289A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant
WO2017150852A1 (fr) Modificateur à base d'azasilane et procédé de préparation d'un polymère à base de diène conjugué modifié à l'aide de celui-ci
WO2021066543A1 (fr) Polymère à base de diène conjugué modifié, son procédé de production, et composition de caoutchouc le comprenant
WO2021107434A1 (fr) Agent de modification, et polymère de diène conjugué modifié produit à l'aide de celui-ci
WO2021010718A1 (fr) Polymère modifié à base d'un diène conjugué, procédé pour sa production et composition de caoutchouc le contenant
WO2017111499A1 (fr) Composé polymère, procédé de préparation d'un polymère à base de diène conjugué modifié l'utilisant, et polymère à base de diène conjugué modifié
WO2017111463A1 (fr) Polymère de diène conjugué modifié, procédé de production associé et modificateur
WO2021060815A1 (fr) Agent de modification, polymère modifié à base de diènes conjugués comprenant celui-ci et procédé de préparation de polymère
WO2016085285A1 (fr) Copolymère styrène-butadiène modifié, son procédé de préparation, et composition de caoutchouc le comprenant
WO2019225824A1 (fr) Polymère à base de diène conjugué modifié et composition de caoutchouc le comprenant

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019520360

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018859974

Country of ref document: EP

Effective date: 20190404

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

Ref document number: 18859974

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE