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WO2018128330A1 - Composé d'amine, polymère de diène conjugué modifié comprenant un groupe fonctionnel dérivé de celui-ci, et méthode de production de polymère de diène conjugué modifié - Google Patents

Composé d'amine, polymère de diène conjugué modifié comprenant un groupe fonctionnel dérivé de celui-ci, et méthode de production de polymère de diène conjugué modifié Download PDF

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Publication number
WO2018128330A1
WO2018128330A1 PCT/KR2017/015670 KR2017015670W WO2018128330A1 WO 2018128330 A1 WO2018128330 A1 WO 2018128330A1 KR 2017015670 W KR2017015670 W KR 2017015670W WO 2018128330 A1 WO2018128330 A1 WO 2018128330A1
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Prior art keywords
conjugated diene
formula
modified conjugated
based polymer
amine compound
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PCT/KR2017/015670
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English (en)
Korean (ko)
Inventor
이상미
손해성
최흥열
김노마
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020170147884A external-priority patent/KR102070382B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP17879654.6A priority Critical patent/EP3378866A4/fr
Priority to JP2018544128A priority patent/JP2019508552A/ja
Priority to US16/066,182 priority patent/US10815314B2/en
Priority to CN201780007028.XA priority patent/CN108541254B/zh
Publication of WO2018128330A1 publication Critical patent/WO2018128330A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • 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
    • C08F236/06—Butadiene
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the present invention relates to a modified conjugated diene-based polymer comprising a functional group derived from a tertiary amine compound represented by Formula 1, a method for preparing the same, and a tertiary amine compound represented by Formula 1 that can be easily used as a modifier of rubber. .
  • a method of reducing the hysteresis loss of the vulcanized rubber In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber.
  • a rebound elasticity of 50 ° C. to 80 ° C., tan ⁇ , 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 ⁇ 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
  • BR or SBR is used as a rubber material for tires
  • fillers such as silica and carbon black are usually blended together in order to obtain required tire properties.
  • the affinity between the BR or SBR and the filler is not good, but there is a problem in that physical properties including wear resistance, crack resistance, or processability are deteriorated.
  • a method for improving the dispersibility of fillers such as SBR and silica or carbon black a method of modifying the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organolithium into a functional group capable of interacting with the filler has been proposed.
  • a method of modifying the polymerizable active end of the conjugated diene polymer with a tin compound, introducing an amino group, or modifying an alkoxysilane derivative has been proposed.
  • the BR or SBR modified by the above-described method has a low terminal denaturation rate, so that the improvement of physical properties is insignificant in a tire manufactured using the same.
  • the present invention has been made to solve the problems of the prior art, an object of the present invention to provide a modified conjugated diene-based polymer comprising a functional group derived from the tertiary amine compound represented by the formula (1).
  • Another object of the present invention is to provide a method for producing a modified conjugated diene polymer using a tertiary amine compound represented by the formula (1).
  • an object of the present invention is to provide a tertiary amine compound represented by the formula (1) which can be easily applied as a modifier for rubber.
  • the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a tertiary amine compound represented by the following formula (1).
  • A is an alkylene group having 1 to 20 carbon atoms
  • X 1 to X 3 are each independently an oxygen element or an alkylene group having 1 to 4 carbon atoms containing an oxygen element.
  • the present invention is to prepare an active polymer having an organic metal bonded to at least one end by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organometallic compound in a hydrocarbon solvent (step 1). ; And it provides a method for producing the modified conjugated diene-based polymer comprising the step (step 2) of reacting the active polymer with a tertiary amine compound represented by the following formula (1).
  • A is an alkylene group having 1 to 20 carbon atoms
  • X 1 to X 3 are each independently an oxygen element or an alkylene group having 1 to 4 carbon atoms containing an oxygen element.
  • the present invention provides a tertiary amine compound represented by the following formula (1).
  • A is an alkylene group having 1 to 20 carbon atoms
  • X 1 to X 3 are each independently an oxygen element or an alkylene group having 1 to 4 carbon atoms containing an oxygen element.
  • the modified conjugated diene-based polymer according to the present invention includes a functional group derived from a tertiary amine compound represented by Chemical Formula 1, such as an amine group and a silane group, thereby having excellent affinity with fillers such as silica-based fillers, and tensile properties. And viscoelastic properties may be excellent.
  • the method for producing a modified conjugated diene-based polymer according to the present invention can easily prepare a modified conjugated diene-based polymer having a high modification rate by using the tertiary amine compound represented by the formula (1) as a modifier.
  • the tertiary amine compound represented by Formula 1 according to the present invention may be used as a modifier for rubber, in particular, a conjugated diene-based polymer to be bonded to the conjugated diene-based polymer chain to provide functional groups such as amine groups and silane groups. have.
  • the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a tertiary amine compound represented by the following Chemical Formula 1.
  • A is an alkylene group having 1 to 20 carbon atoms
  • X 1 to X 3 are each independently an oxygen element or an alkylene group having 1 to 4 carbon atoms containing an oxygen element.
  • A is an alkylene group having 1 to 10 carbon atoms
  • X 1 to X 3 may be independently an alkylene group having 1 to 2 carbon atoms including an oxygen element or an oxygen element.
  • tertiary amine compound represented by Formula 1 may be represented by Formula 2.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by reacting the active polymer to which the organic metal is bonded and the tertiary amine compound represented by Formula 1 through the manufacturing method described below, the modification
  • the conjugated diene polymer may have improved physical properties by including a functional group derived from a tertiary amine compound represented by Chemical Formula 1.
  • the modified conjugated diene-based polymer may include a filler affinity functional group and a solvent affinity functional group by including a functional group derived from a tertiary amine compound represented by Chemical Formula 1, and a rubber composition comprising the same and prepared therefrom Wear resistance, low fuel efficiency and workability of molded articles such as used tires can be improved.
  • the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 100,000 g / mol to 2,000,000 g / mol, specifically 150,000 g / mol to 1,000,000 g / mol.
  • Mn number average molecular weight
  • the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 100,000 g / mol to 5,000,000 g / mol, specifically 200,000 g / mol to 2,000,000 g / mol.
  • Mw weight average molecular weight
  • the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1.0 to 3.0, when it is applied to the rubber composition can be improved in tensile properties and viscoelasticity.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention has a weight distribution range as described above when considering the good effect of balancing the mechanical properties, elastic modulus and processability of the rubber composition when applied to the rubber composition
  • the average molecular weight and the number average molecular weight may be one that satisfies the conditions of the aforementioned range at the same time.
  • the modified conjugated diene-based polymer may have a molecular weight distribution of 3.0 or less, a weight average molecular weight of 100,000 g / mol to 5,000,000 g / mol, a number average molecular weight of 100,000 g / mol to 2,000,000 g / mol More specifically, the molecular weight distribution may be 2.5 or less, a weight average molecular weight of 200,000 g / mol to 2,000,000 g / mol, and a number average molecular weight of 150,000 g / mol to 1,000,000 g / mol.
  • 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).
  • the said number average molecular weight is a common average of the individual polymer molecular weights which measured the molecular weight of n polymer molecules, calculated
  • the modified conjugated diene-based polymer includes a functional group derived from the tertiary amine compound represented by Formula 1, polystyrene reduced weight average molecular weight (Mw) analyzed by gel permeation chromatography
  • Mw polystyrene reduced weight average molecular weight
  • Mn The molecular weight distribution (Mw / Mn) is 1.30 to 2.50, and the ratio (Mw / Mp) of the weight average molecular weight (Mw) and the peak top molecular weight (Mp) is 0.70 to 1.125. It may be.
  • the peak top molecular weight (Mp) represents the molecular weight at the maximum peak.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may be a polymer having a high linearity of the value of -S / R (stress / relaxation) at 100 °C 0.5 or more.
  • the -S / R represents a change in the stress (stress) that occurs in response to 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 the lower the linearity of the polymer.
  • the lower the linearity the higher the rolling resistance or rolling resistance when applied to the rubber composition.
  • the degree of branching and molecular weight distribution of the polymer can be predicted from the value of -S / R.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention has a high -S / R value of 0.5 or more at 100 °C as described above, when applied to a rubber composition may be excellent in resistance and fuel economy characteristics.
  • the modified conjugated diene-based polymer -S / R value may be 0.5 to 1.5.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) of 40 to 200 at 100 °C, specifically 40 to 100 or 60 to 150 can be have.
  • MV Mooney viscosity
  • the modified conjugated diene-based polymer according to the present invention may be excellent in workability by having a Mooney viscosity of the above-described range.
  • the Mooney viscosity was measured at a condition of 100 °C and Rotor Speed 2 ⁇ 0.02rpm using a Mooney viscometer, for example, Large Rotor of Monsanto MV2000E.
  • a Mooney viscometer for example, Large Rotor of Monsanto MV2000E.
  • the polymer is allowed to stand at room temperature (23 ⁇ 5 ° C.) for at least 30 minutes, and then 27 ⁇ 3 g is taken and filled into the die cavity, and platen is operated to measure the Mooney viscosity while applying torque.
  • the -S / R value was obtained by measuring the inclination value of the Mooney viscosity change appearing as the torque is released after the non-viscosity measurement and obtained as an absolute value thereof.
  • the present invention provides a method for producing a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the formula (1).
  • the production method according to an embodiment of the present invention is to polymerize a conjugated diene-based monomer or an aromatic vinyl monomer and a conjugated diene-based monomer in the presence of an organometallic compound in a hydrocarbon solvent to form an active polymer having an organometallic bonded to at least one end thereof.
  • A is an alkylene group having 1 to 20 carbon atoms
  • X 1 to X 3 are each independently an oxygen element or an alkylene group having 1 to 4 carbon atoms containing an oxygen element.
  • tertiary amine compound represented by Formula 1 may be as described above.
  • Step 1 is a step for preparing an active polymer in which an organometallic is bonded to at least one end, and may be performed by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organometallic compound in a hydrocarbon solvent.
  • the polymerization of step 1 may be one using a conjugated diene monomer alone or an aromatic vinyl monomer and a conjugated diene monomer together as described above. That is, the polymer prepared by the above production method according to an embodiment of the present invention may be a homopolymer derived from a conjugated diene monomer or a copolymer derived from an aromatic vinyl monomer and a conjugated diene monomer.
  • the conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.
  • the 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 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 has a unit derived from conjugated diene monomer in the prepared modified conjugated diene-based polymer, specifically, May be used in an amount to include from 60% to 90% by weight, more specifically from 60% to 85% by weight.
  • 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 organometallic compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.
  • the organometallic compound is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, phenyl Lithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl It may be one or more selected from the group consisting of sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium
  • 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.
  • the adiabatic polymerization refers to a polymerization method including the step of polymerizing with a self-heating reaction without adding heat after the addition of the multifunctional anion polymerization initiator, and the isothermal polymerization is optionally after adding the polyfunctional anion polymerization initiator It refers to a polymerization method in which the temperature of the polymer is kept constant by applying heat 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 for coupling the functional group derived from the tertiary amine compound represented by Formula 1 to the polymerization chain by reacting the active polymer and the tertiary amine compound represented by Formula 1.
  • the tertiary amine compound represented by Formula 1 may be used in a ratio of 0.01 mol to 5 mol relative to 1 mol of the organometallic compound.
  • Step 2 is a modification reaction for introducing a functional group into the polymer chain, it may be to perform the reaction for 1 minute to 5 hours at 0 °C to 120 °C.
  • modified conjugated diene-based polymer manufacturing method may be carried out by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.
  • an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like can be added to the polymerization reaction system to terminate the polymerization reaction.
  • BHT 2,6-di-t-butyl-p-cresol
  • the modified conjugated diene-based polymer may be obtained through desolvent treatment or vacuum drying such as steam stripping to lower the partial pressure of the solvent through supply of steam.
  • the reaction product obtained as a result of the above-described modification reaction may include an active polymer, which is not modified, together with the above-mentioned modified conjugated diene polymer.
  • 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.
  • the present invention provides a tertiary amine compound represented by the formula (1) that can be easily applied as a modifier for rubber.
  • the tertiary amine compound according to an embodiment of the present invention may be represented by the following formula (1).
  • A is an alkylene group having 1 to 20 carbon atoms
  • X 1 to X 3 are each independently an oxygen element or an alkylene group having 1 to 4 carbon atoms containing an oxygen element.
  • the tertiary amine compound represented by Chemical Formula 1 includes a reactive functional group, a filler affinity functional group and a solvent affinity functional group for the conjugated diene-based polymer, thereby easily modifying the conjugated diene-based polymer at a high modification rate. It is possible to improve the wear resistance, low fuel consumption characteristics and workability of the rubber composition and the molded article such as a tire manufactured therefrom.
  • the tertiary amine compound represented by Chemical Formula 1 may include an amine group which is a reactive functional group for the polymer in the molecule as described above, and the reactive functional group may have high reactivity with respect to the active site of the conjugated diene-based polymer.
  • the conjugated diene-based polymer can be modified with high modification rate, and as a result, the functional functional group can be introduced into the conjugated diene-based polymer in high yield.
  • the amine group may be further reacted with the conjugated diene-based polymer terminal to be converted into a primary or secondary amino group to further improve affinity with the filler, particularly carbon black.
  • the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a molded article prepared from the rubber composition.
  • the rubber composition according to an embodiment of the present invention is 0.1 to 100% by weight of the modified conjugated diene-based polymer, specifically 10 to 100% by weight, more specifically 20 to 90% by weight It may be to include. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, improvement effects such as abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.
  • the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition.
  • the modified conjugated diene copolymer may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight.
  • the rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene),
  • the rubber composition may include a 0.1 to 150 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, carbon black or a combination thereof. Specifically, the filler may be carbon carbon rack.
  • the carbon black filler is not particularly limited, for example, the nitrogen adsorption specific surface area (measured based on N 2 SA, JIS K 6217-2: 2001) may be 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.
  • DBP dibutyl phthalate oil absorption
  • the nitrogen adsorption specific surface area of the carbon black exceeds 250 m 2 / g, the workability of the rubber composition may be lowered. If the carbon black has a specific surface area of less than 20 m 2 / g, the reinforcing performance by the carbon black may be insignificant.
  • the DBP oil absorption of the carbon black exceeds 200 cc / 100 g, the workability of the rubber composition may be lowered. If the DBP oil absorption of the carbon black is less than 80 cc / 100 g, the reinforcement performance of the carbon black may be insignificant.
  • the silica is not particularly limited, but may be, for example, wet silica (silicate silicate), dry silica (silicate anhydride), calcium silicate, aluminum silicate or colloidal silica.
  • the silica may be a wet silica having the most remarkable effect of improving the fracture characteristics and a wet grip.
  • the silica has a nitrogen adsorption specific surface area (N 2 SA) of 120 m 2 / g to 180 m 2 / g, and CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m 2 / g to 200 m 2 / g.
  • N 2 SA nitrogen adsorption specific surface area
  • CTAB cetyl trimethyl ammonium bromide
  • the nitrogen adsorption specific surface area of the silica is less than 120 m 2 / g, the reinforcing performance by silica may be deteriorated.
  • the nitrogen adsorption specific surface area is less than 180 m 2 / g, the workability of the rubber composition may be deteriorated.
  • the CTAB adsorption specific surface area of the silica is less than 100 m 2 / g, reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 / g, the workability of the rubber composition may be deteriorated.
  • silica when silica is used as the filler, 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.
  • the amount of the silane coupling agent used 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 filler.
  • the silane coupling agent may be used in 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.
  • the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.
  • the vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.
  • the rubber composition according to an embodiment of the present invention in addition to the above components, various additives commonly used in the rubber industry, in particular, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
  • the 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 molded article manufactured using the rubber composition may include a tire or a tire tread.
  • Example 1 0.5 mol of tri (2- (2,8,9-trioxa-5-aza-1-silabicyclo [3.3.3] undecane-1-yl) ethyl) amine was added to denature the compound.
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the reaction was carried out.
  • Example 1 1.2 mol of tri (2- (2,8,9-trioxa-5-aza-1-silabicyclo [3.3.3] undecane-1-yl) ethyl) amine was added to denature the compound.
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the reaction was carried out.
  • Example 1 0.2 mol of tri (2- (2,8,9-trioxa-5-aza-1-silabicyclo [3.3.3] undecane-1-yl) ethyl) amine was added to denature the compound.
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the reaction was carried out.
  • Example 1 chlorodimethylsilane (instead of tri (2- (2,8,9-trioxa-5-aza-1-silabicyclo [3.3.3] undecane-1-yl) ethyl) amine
  • a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the modification reaction was performed using chlorodimethylsilane.
  • SM Styrene derived units
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each copolymer were measured by gel permeation chromatograph (GPC) analysis under 40 ° C.
  • the column (column) was used in combination with two bags of PLgel Olexis of Polymer Laboratories Co., Ltd. and one PLgel mixed-C column, all of the newly replaced column was a mixed bed column.
  • PS polystyrene
  • the polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by the above method.
  • the Mooney viscosity of each copolymer was measured by MV-2000 (Alpha Technologies Co., Ltd.) for 15 minutes or more of each sample weight 15g or more for 1 minute and then at 100 °C for 4 minutes.
  • Each rubber composition was prepared through a first stage kneading process and a second stage kneading process.
  • the amount of the material excluding the copolymer is shown based on 100 parts by weight of the modified conjugated diene copolymer.
  • the first stage kneading 137.5 parts by weight of each copolymer, 70 parts by weight of silica, and 11.2 parts by weight of bis (3-triethoxysilylpropyl) tetrasulfide as a silane coupling agent using a half-barrier with temperature controller.
  • Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester to obtain tensile strength and tensile stress at 300% elongation.
  • the viscoelastic properties were measured by using a dynamic mechanical analyzer (TA Co., Ltd.) in the torsion mode to measure the deformation of Tan ⁇ by changing the strain at a frequency of 10 Hz and measuring temperature (-60 °C ⁇ 60 °C). It is represented by the exponential index as a reference value. In this case, the exponentiation was calculated through Equations 1 and 2 below.
  • Equations 1 and 2 reference values are measured values of Comparative Example 1, and measured values are measured values of the remaining Examples and Comparative Examples.
  • the styrene-butadiene copolymer of Comparative Example 1 in which the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 to 4 prepared using the modifying agent according to one embodiment of the present invention is not modified Tan ⁇ at 0 ° C. was increased (Index value improved) and Tan at 60 ° C. compared with the rubber composition comprising the modified styrene-butadiene copolymer of Comparative Example 2 modified with a rubber composition and a conventional modifier It was confirmed that the value of ⁇ decreased (Index value improved). This is a result showing that the modified styrene-butadiene copolymer prepared by using the modifier according to an embodiment of the present invention has excellent resistance and rolling resistance characteristics on wet road surface, and high fuel efficiency.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un polymère de diène conjugué modifié comprenant un groupe fonctionnel dérivé d'un composé d'amine tertiaire représenté par la formule chimique 1, une méthode de production de celui-ci, et un composé d'amine tertiaire représenté par la formule chimique 1.
PCT/KR2017/015670 2017-01-06 2017-12-28 Composé d'amine, polymère de diène conjugué modifié comprenant un groupe fonctionnel dérivé de celui-ci, et méthode de production de polymère de diène conjugué modifié WO2018128330A1 (fr)

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EP17879654.6A EP3378866A4 (fr) 2017-01-06 2017-12-28 Composé d'amine, polymère de diène conjugué modifié comprenant un groupe fonctionnel dérivé de celui-ci, et méthode de production de polymère de diène conjugué modifié
JP2018544128A JP2019508552A (ja) 2017-01-06 2017-12-28 アミン化合物、これから由来された官能基を含む変性共役ジエン系重合体、及び変性共役ジエン系重合体の製造方法
US16/066,182 US10815314B2 (en) 2017-01-06 2017-12-28 Amine compound, modified conjugated diene-based polymer containing functional group derived therefrom, and method of preparing the modified conjugated diene-based polymer
CN201780007028.XA CN108541254B (zh) 2017-01-06 2017-12-28 胺化合物、包含由其衍生的官能团的改性共轭二烯类聚合物、以及该聚合物的制备方法

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KR1020170147884A KR102070382B1 (ko) 2017-01-06 2017-11-08 아민 화합물, 이로부터 유래된 작용기를 포함하는 변성 공액디엔계 중합체 및 변성 공액디엔계 중합체의 제조방법
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US10947380B2 (en) 2018-12-20 2021-03-16 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire
CN112805309A (zh) * 2019-07-15 2021-05-14 株式会社Lg化学 改性共轭二烯类聚合物、其制备方法和包含其的橡胶组合物
US11208518B2 (en) 2018-12-11 2021-12-28 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire

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Publication number Priority date Publication date Assignee Title
US11208518B2 (en) 2018-12-11 2021-12-28 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire
US10947380B2 (en) 2018-12-20 2021-03-16 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire
CN112805309A (zh) * 2019-07-15 2021-05-14 株式会社Lg化学 改性共轭二烯类聚合物、其制备方法和包含其的橡胶组合物
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