WO2018105920A1 - 변성제 및 이로부터 유래된 작용기를 포함하는 변성 공액디엔계 중합체 - Google Patents
변성제 및 이로부터 유래된 작용기를 포함하는 변성 공액디엔계 중합체 Download PDFInfo
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- WO2018105920A1 WO2018105920A1 PCT/KR2017/013130 KR2017013130W WO2018105920A1 WO 2018105920 A1 WO2018105920 A1 WO 2018105920A1 KR 2017013130 W KR2017013130 W KR 2017013130W WO 2018105920 A1 WO2018105920 A1 WO 2018105920A1
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- 0 C*(N(C)C)O*(*)C(OO)=O Chemical compound C*(N(C)C)O*(*)C(OO)=O 0.000 description 1
- OXIXEBSZJICKIJ-UHFFFAOYSA-N CCCCCOC(N(CC1)CCN1[Si+](C)(C)C)=O Chemical compound CCCCCOC(N(CC1)CCN1[Si+](C)(C)C)=O OXIXEBSZJICKIJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and 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
- C08F36/04—Homopolymers and 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
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Definitions
- the present invention relates to a modifier represented by the formula (1), a modified conjugated diene-based polymer of a high modification rate containing the functional group derived from the modifier, a method for producing the polymer.
- 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, and an object thereof is to provide a modifier useful for polymer modification.
- Still another object of the present invention is to provide a modified conjugated diene-based polymer having a high modification rate including the functional group derived from the modifier.
- Another object of the present invention is to provide a method for producing the modified conjugated diene polymer.
- the present invention provides a modifier represented by the following formula (1).
- R 1 , R 2 and R 5 are each independently substituted or unsubstituted with one or more substituents 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.
- substituents 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 independently of each other a C 1 to C 20 divalent hydrocarbon group unsubstituted or substituted with an alkyl group of 1 to 20 carbon atoms,
- n is an integer of 1-3.
- the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).
- R 1 , R 2 and R 5 are each independently substituted or unsubstituted with one or more substituents 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.
- substituents 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 independently of each other a C 1 to C 20 divalent hydrocarbon group unsubstituted or substituted with an alkyl group of 1 to 20 carbon atoms,
- n is an integer of 1-3.
- the present invention comprises the steps of polymerizing the conjugated diene-based monomer in the presence of a catalyst composition comprising a lanthanum-based rare earth element-containing 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 modifier represented by the formula (1).
- the modifying agent represented by Formula 1 according to the present invention has a high anion reactivity due to the introduction of a polymer reactive functional group, such as an ester group, and thus can easily act with the active site of the polymer.
- modified conjugated diene-based polymer according to the present invention may be excellent in affinity with a filler such as carbon black by including a modifier-derived functional group represented by the formula (1).
- 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 a modifier represented by the formula (1).
- the present invention provides a modifier useful for the modification of the modified conjugated diene-based polymer.
- the denaturing agent according to an embodiment of the present invention is characterized in that represented by the following formula (1).
- R 1 , R 2 and R 5 are each independently substituted or unsubstituted with one or more substituents 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.
- substituents 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 independently of each other a C 1 to C 20 divalent hydrocarbon group unsubstituted or substituted with an alkyl group of 1 to 20 carbon atoms,
- n is an integer of 1-3.
- R 1 , R 2 and R 5 are independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 1 , R 2 and R 5 is substituted with a substituent R 1 , R 2 and R 5 are each independently a C 1-20 alkyl group, a C 3-20 cycloalkyl group and a C 6-20 aryl group. It may be an alkyl group having 1 to 20 carbon atoms substituted with one or more selected substituents.
- R 1 , R 2, and R 5 are each independently substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms. It may be an alkyl group having 1 to 10 carbon atoms, and more specifically, may be an alkyl group having 1 to 10 carbon atoms substituted with an alkyl group having 1 to 10 carbon atoms.
- the R 1 , R 2 and R 5 may be an unsubstituted alkyl group having 1 to 20 carbon atoms, specifically, an alkyl group having 1 to 10 carbon atoms, and more specifically an alkyl group having 1 to 6 carbon atoms. It may be
- R 3 and R 4 independently of each other substituted or unsubstituted carbon atoms of 1 to 20 carbon atoms substituted with an alkyl group, and R 3 and R 4 substituted with an alkyl group 2 to 1 to 20 carbon atoms
- R 3 and R 4 may be independently an alkylene group having 1 to 10 carbon atoms substituted with an alkyl group having 1 to 10 carbon atoms
- R 3 and R 4 may be independently selected from 1 to 10 carbon atoms. It may be an alkylene group having 1 to 6 carbon atoms substituted with an alkyl group of 6.
- R 3 and R 4 when R 3 and R 4 are independently an unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, R 3 and R 4 may be independently an alkylene group of 1 to 10 and , may be specifically, the R 3 and R 4 are, independently of each other may be an alkylene date of 1 to 6 carbon atoms, and more specifically to the R 3 and R 4 are together an alkylene group having 1 to 3 carbon atoms with each other.
- R 1 , R 2 and R 3 are independently an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, and R 3 and R 4 are independent of each other N may be an alkylene group having 1 to 6 carbon atoms, n may be an integer of 1 to 3, and more specifically, in Chemical Formula 1, R 1 , R 2, and R 3 may be each independently an alkyl group having 1 to 10 carbon atoms, R 3 and R 4 are independently of each other an alkylene group having 1 to 6 carbon atoms, n may be an integer of 1 to 3.
- Chemical Formula 1 may be represented by Chemical Formula 1-1 to Chemical Formula 1-5.
- the denaturant may be one having a solubility of at least 10 g in a nonpolar solvent such as 100 g of normal hexane at 25 ° C. and 1 atmosphere.
- the solubility of the denaturant means the degree of clear dissolution without a hazy phenomenon when observed by the naked eye.
- the modifier according to an embodiment of the present invention can be used as a modifier for the polymer to improve the modification rate of the polymer.
- the modifying agent represented by the formula (1) according to the present invention can be easily modified to a high modification rate of the conjugated diene polymer by including a reactive functional group, a filler affinity functional group and a solvent affinity functional group for the conjugated diene-based polymer
- the denaturant of Chemical Formula 1 may include an ester group and an amine group, which are reactive functional groups for the polymer, as described above, and the reactive functional groups exhibit high reactivity with respect to the active site of the conjugated diene-based polymer.
- the conjugated diene-based polymer can be modified at a high modification rate, and consequently, a functional group substituted with the modifier can be introduced into the conjugated diene-based polymer at a 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 modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).
- R 1 , R 2 and R 5 are each independently substituted or unsubstituted with one or more substituents 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.
- substituents 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 independently of each other a C 1 to C 20 divalent hydrocarbon group unsubstituted or substituted with an alkyl group of 1 to 20 carbon atoms,
- n is an integer of 1-3.
- the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by reacting the active polymer and the modifier represented by the formula (1) through the manufacturing method described below, the modified conjugated diene-based polymer is the formula 1 Physical properties may be improved by including a modifier-derived functional group represented by.
- the modifier represented by Formula 1 may be as described above.
- the modified conjugated diene-based polymer may include a filler affinity functional group and a solvent affinity functional group by including a modifier-derived functional group represented by the formula (1), a rubber composition comprising the same, and a tire prepared therefrom. Wear resistance, low fuel consumption characteristics and workability of the molded article can be improved.
- the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 100,000 g / mol to 500,000 g / mol, specifically 100,000 g / mol to 400,000 g / mol.
- Mn number average molecular weight
- the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 300,000 g / mol to 1,000,000 g / mol, specifically 400,000 g / mol to 1,000,000 g / mol.
- Mw weight average molecular weight
- the modified conjugated diene-based polymer may have a narrow molecular weight distribution (Mw / Mn), specifically, the molecular weight distribution of the modified conjugated diene-based polymer may be 2.0 to 3.0.
- the modified conjugated diene-based polymer according to an embodiment of the present invention may have a narrow molecular weight distribution as described above, thereby improving tensile properties and viscoelasticity of the rubber composition and the rubber specimen to which the modified conjugated diene polymer is applied.
- 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 polymer may have a molecular weight distribution of 3.0 or less, a weight average molecular weight of 300,000 g / mol to 1,000,000 g / mol, and a number average molecular weight of 100,000 g / mol to 500,000 g / mol.
- the molecular weight distribution may be 2.8 or less, a weight average molecular weight of 400,000 g / mol to 1,000,000 g / mol, and a number average molecular weight of 100,000 g / mol to 400,000 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).
- GPC gel permeation chromatography
- 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 0.7 °C or more.
- the -S / R represents a change in the stress (stress) in response to the same amount of strain generated in the material, it 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 lower the value of -S / R the higher the degree of branching, the broader molecular weight distribution, and as a result, the processability of the polymer is excellent while Characteristics are low.
- the modified conjugated diene-based polymer according to an embodiment of the present invention has a high -S / R value of 0.7 or more at 100 °C as described above, when applied to the rubber composition may be excellent in resistance properties and fuel economy characteristics.
- the -S / R value of the modified conjugated diene-based polymer may be 0.7 to 1.0.
- the -S / R value was measured under a condition of 100 ° C. and a Rotor Speed of 2 ⁇ 0.02 rpm using a Mooney Viscometer, for example, a Large Rotor of Monsanto MV2000E. Specifically, the polymer is allowed to stand at room temperature (23 ⁇ 5 ° C.) for at least 30 minutes, and then 27 ⁇ 3 g is collected and filled into the die cavity, and the platen is operated to measure the Mooney viscosity while applying torque. The -S / R value was obtained by measuring the slope value of the Mooney viscosity change appearing as the torque was released.
- the modified conjugated diene-based polymer may have a cis-1,4 bond content of 95% or more, more specifically 96% or more of the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR).
- FT-IR Fourier transform infrared spectroscopy
- the modified conjugated diene-based polymer may have a vinyl content of 5% or less, more specifically 2% or less, as measured by Fourier transform infrared spectroscopy.
- vinyl content in the polymer exceeds 5%, there is a fear that the wear resistance, crack resistance, and ozone resistance of the rubber composition including the same deteriorate.
- the cis-1,4 bond content and vinyl content in the polymer by the Fourier Transform Infrared Spectroscopy are conjugated diene polymers prepared at a concentration of 5 mg / mL by blanking carbon disulfide in the same cell.
- the maximum peak value (a, baseline) near 1130 cm ⁇ 1 of the measurement spectrum, and the smallest peak near 967 cm ⁇ 1 indicating a trans-1,4 bond Each content is determined using the value (b), the minimum peak value (c) near 911 cm -1 representing vinyl bonds, and the minimum peak value (d) near 736 cm -1 representing cis-1,4 bonds. I got it.
- the present invention provides a method for producing a modified conjugated diene-based polymer comprising a modifier derived group represented by the formula (1).
- the preparation method according to an embodiment of the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene monomer in the presence of a catalyst composition comprising a lanthanum-based rare earth element-containing compound in a hydrocarbon solvent (step 1); And reacting the active polymer with a denaturant represented by Formula 1 below (step 2).
- R 1 , R 2 and R 5 are each independently substituted or unsubstituted with one or more substituents 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.
- substituents 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 independently of each other a C 1 to C 20 divalent hydrocarbon group unsubstituted or substituted with an alkyl group of 1 to 20 carbon atoms,
- n is an integer of 1-3.
- the modifier represented by Formula 1 may be as described above.
- Step 1 is a step for preparing an active metal combined with an organic metal using a catalyst composition comprising a lanthanum-based rare earth element-containing compound, which is performed by polymerizing a conjugated diene monomer in the presence of the catalyst composition in a hydrocarbon solvent.
- a catalyst composition comprising a lanthanum-based rare earth element-containing compound, which is performed by polymerizing a conjugated diene monomer in the presence of the catalyst composition in a hydrocarbon solvent.
- 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 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 catalyst composition may be used in an amount such that the lanthanum-based rare earth element-containing compound is 0.1 mmnol to 0.5 mmol based on 100 g of the total conjugated diene-based monomer, and specifically, the lanthanum-based rare earth element-containing compound is conjugated diene. It may be used in an amount such that 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol, based on 100 g of the total monomers.
- the lanthanum-based rare earth element-containing compound is not particularly limited, but may be any one or two or more compounds of atomic number 57 to 71 rare earth metals such as lanthanum, neodymium, cerium, gadolinium or praseodymium, and more specifically, neodymium It may be a compound containing at least one selected from the group consisting of, lanthanum and gadolinium.
- the lanthanum-based rare earth element-containing compound is a rare earth element-containing carboxylate (for example, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium acetate, neodymium gluconate, neodymium citrate, neodymium fumarate, Neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate and the like); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodym
- neodymium butyl phosphonate neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methylheptyl) phosphonate, Neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate, and the like); Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium oc
- the lanthanum-based rare earth element-containing compound may include a neodymium-based compound represented by Formula 3 below.
- R a to R c may be independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that R a to R c are not all hydrogen at the same time.
- the neodymium compound may be Nd (neodecanoate) 3 , Nd (2-ethylhexanoate) 3 , Nd (2,2-diethyl decanoate) 3 , Nd (2,2-dipropyl Decanoate) 3 , Nd (2,2-dibutyl decanoate) 3 , Nd (2,2-dihexyl decanoate) 3 , Nd (2,2-dioctyl decanoate) 3 , Nd ( 2-ethyl-2-propyl decanoate) 3 , Nd (2-ethyl-2-butyl decanoate) 3 , Nd (2-ethyl-2-hexyl decanoate) 3 , Nd (2-propyl-2 -Butyl decanoate) 3 , Nd (2-propyl-2-hexyl decanoate) 3 , Nd (2-propyl-2 -Butyl decan
- the lanthanum-based rare earth element-containing compound is more specifically represented by Chemical Formula 3 in view of excellent solubility in a polymerization solvent, conversion to catalytic active species, and thus an improvement in catalytic activity without concern for oligomerization.
- R a is a linear or branched alkyl group having 4 to 12 carbon atoms
- R b and R c are independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R b and R c are neodymium compounds Can be.
- R a is a linear or branched alkyl group having 6 to 8 carbon atoms
- R b and R c may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R b And R c may not be hydrogen at the same time
- specific examples include Nd (2,2-diethyl decanoate) 3 , Nd (2,2-dipropyl decanoate) 3 , Nd (2,2-di Butyl decanoate) 3 , Nd (2,2-dihexyl decanoate) 3 , Nd (2,2-dioctyl decanoate) 3 , Nd (2-ethyl-2-propyl decanoate) 3 , Nd (2-ethyl-2-butyl decanoate) 3 , Nd (2-ethyl-2-hexyl decanoate) 3 , Nd (2-propyl-2-butyl decanoate) 3 ,
- R a may be a linear or branched alkyl group having 6 to 8 carbon atoms
- R b and R c may each independently be an alkyl group having 2 to 6 carbon atoms.
- the neodymium-based compound represented by Chemical Formula 3 includes a carboxylate ligand including an alkyl group having various lengths of 2 or more carbon atoms at the ⁇ (alpha) position as a substituent, thereby inducing steric changes around the neodymium center metal. It is possible to block the entanglement of the liver, whereby there is an effect that can suppress the oligomerization.
- such a neodymium-based compound has a high solubility in the polymerization solvent, the rate of neodymium is located in the central portion that is difficult to convert to the catalytic active species is reduced, there is a high conversion rate to the catalytic active species.
- solubility of the lanthanum-based rare earth element-containing compound according to an embodiment of the present invention may be about 4 g or more per 6 g of nonpolar solvent at room temperature (25 ° C.).
- the solubility of the neodymium-based compound means the degree of clear dissolution without turbid phenomenon, it can exhibit excellent catalytic activity by showing such a high solubility.
- the lanthanum-based rare earth element-containing compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base.
- This reactant has the effect of improving the solubility of the lanthanum series rare earth element-containing compound in the solvent with a Lewis base and storing it in a stable state for a long time.
- the Lewis base may be used in an amount of 30 mol or less, or 1 to 10 mol, for example, per mol of rare earth elements.
- the Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenylether, triethylamine, organophosphorus compound or monovalent or dihydric alcohol and the like.
- the catalyst composition may further include at least one of (a) an alkylating agent, (b) a halide, and (c) a conjugated diene monomer together with a lanthanum-based rare earth element-containing compound.
- the alkylating agent may serve as a cocatalyst composition as an organometallic compound capable of transferring a hydrocarbyl group to another metal.
- the alkylating agent can be used without particular limitation as long as it is usually used as an alkylating agent in the preparation of the diene polymer, and is soluble in a polymerization solvent, such as, for example, an organoaluminum compound, an organic magnesium compound, or an organolithium compound. It may be an organometallic compound containing.
- organoaluminum compound trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentyl Alkyl aluminum, such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, Diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride
- organic magnesium compound examples include alkylmagnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or dibenzylmagnesium.
- organolithium compound examples include alkyl lithium compounds such as n-butyllithium.
- the organoaluminum compound may be aluminoxane.
- the aluminoxane may be prepared by reacting a trihydrocarbyl aluminum compound with water, and specifically, may be a linear aluminoxane of Formula 4a or a cyclic aluminoxane of Formula 4b.
- R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and x and y are each independently an integer of 1 or more, specifically 1 to 100 More specifically, it may be an integer of 2 to 50.
- the aluminoxane is methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n Pentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane or 2,6- Dimethylphenyl aluminoxane and the like, and any one or a mixture of two or more thereof may be
- the modified methyl aluminoxane is a methyl group of methyl aluminoxane is substituted with a modification group (R), specifically a hydrocarbon group having 2 to 20 carbon atoms, specifically, may be a compound represented by the following formula (5).
- R is as defined above, m and n may be an integer of 2 or more independently of each other.
- Me represents a methyl group.
- R is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may be an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an allyl group or an alkynyl group having 2 to 20 carbon atoms, and more specifically, has 2 carbon atoms such as an ethyl group, an isobutyl group, a hexyl group, an octyl group, or the like. It is an alkyl group of 10 to 10, and may be an isobutyl group more specifically.
- the modified methyl aluminoxane may be obtained by substituting about 50 mol% to 90 mol% of the methyl group of methyl aluminoxane with the aforementioned hydrocarbon group.
- the content of the substituted hydrocarbon group in the modified methylaluminoxane is within the above range, it is possible to promote the alkylation to increase the catalytic activity.
- Such modified methylaluminoxane may be prepared according to a conventional method, specifically, may be prepared using alkyl aluminum other than trimethylaluminum and trimethylaluminum.
- the alkyl aluminum may be triisobutyl aluminum, triethyl aluminum, trihexyl aluminum, trioctyl aluminum, or the like, and any one or a mixture of two or more thereof may be used.
- the catalyst composition according to an embodiment of the present invention is a 1 to 200 molar ratio, specifically 1 to 100 molar ratio, more specifically 3 to 20 molar ratio of the alkylating agent relative to 1 mole of the lanthanum-based rare earth element-containing compound. It may be to include. If the alkylating agent is included in an amount exceeding 200 molar ratio, it is not easy to control the catalytic reaction during the preparation of the polymer, and the excess alkylating agent may cause side reactions.
- the halide is not particularly limited, and examples thereof include a halogen alone, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetal halide, a metal halide, or an organometallic halide.
- a halogen alone, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetal halide, a metal halide, or an organometallic halide One or more than one mixture may be used.
- any one or two or more mixtures selected from the group consisting of an organic halide, a metal halide and an organometallic halide may be used as the halide.
- halogen examples include fluorine, chlorine, bromine or iodine.
- interhalogen compounds include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.
- the hydrogen halide may include hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.
- the organic halides include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, tri Phenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propy Onyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called
- non-metal halides include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl 4 ), silicon tetrabromide , Arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon iodide, arsenic triiode, tellurium iodide, boron triiodide, phosphorus triiode, phosphorus oxyiodide or phosphorus iodide Can be mentioned.
- the metal halide may be tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony trichloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, Indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiode, gallium iodide, indium trioxide, titanium iodide, zinc iodide, zinc iodide Germanium, tin iodide, tin iodide, antimony triiodide or magnesium iodide.
- the organometallic halide may be dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride.
- the catalyst composition according to an embodiment of the present invention is 1 to 20 moles, more specifically 1 to 5 moles, more specifically 2 to the halide relative to 1 mole of the lanthanum-based rare earth element-containing compound Moles to 3 moles. If the halide is contained in excess of 20 molar ratios, the catalytic reaction may not be easily removed, and an excess of halide may cause side reactions.
- the catalyst composition for preparing a conjugated diene polymer according to an embodiment of the present invention may include a non-coordinating anion-containing compound or a non-coordinating anion precursor compound instead of or together with the halide.
- the non-coordinating anion is a steric bulky anion that does not form a coordination bond with the active center of the catalyst system due to steric hindrance, and is a tetraarylborate anion or a tetraaryl fluoride Borate anions and the like.
- the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together with the above non-coordinating anion; It may include an ammonium cation such as an N, N-dialkyl aninium cation, or a counter cation such as a phosphonium cation.
- the compound containing the non-coordinating anion is triphenyl carbonium tetrakis (pentafluoro phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluoro phenyl) borate, triphenyl carbonium tetra Kiss [3,5-bis (trifluoromethyl) phenyl] borate, or N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.
- non-coordinating anion precursor as a compound capable of forming non-coordinating anions under reaction conditions, a triaryl boron compound (BE 3 , where E is a pentafluorophenyl group or a 3,5-bis (trifluoromethyl) phenyl group or the like) The same strong electron-withdrawing aryl group).
- the catalyst composition may further include a conjugated diene monomer, and a prepolymerization catalyst composition in which a part of the conjugated diene monomer used in the polymerization reaction is premixed with the catalyst composition for polymerization.
- the catalyst composition activity can be improved and the conjugated diene polymer to be produced can be stabilized.
- the "preforming” is a catalyst composition comprising a lanthanum-based rare earth element-containing compound, an alkylating agent and a halide, i.e., when diisobutylaluminum hydride (DIBAH) is included in the catalyst system.
- DIBAH diisobutylaluminum hydride
- a small amount of conjugated diene-based monomers such as 1,3-butadiene is added to reduce the possibility of generating various catalyst compositions active species, and pre-polymerization is performed in the catalyst composition system with addition of 1,3-butadiene. It may mean.
- premix may refer to a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.
- the conjugated diene monomer used in the preparation of the catalyst composition may be a part of the amount used within the total amount of the conjugated diene monomer used in the polymerization reaction, for example, the lanthanum-based rare earth element-containing compound 1 It may be used to 1 to 100 moles, specifically 10 to 50 moles, or 20 to 50 moles per mole.
- the catalyst composition according to an embodiment of the present invention is at least one of the above-described lanthanum-based rare earth element-containing compound and alkylating agent, halide and conjugated diene-based monomer in an organic solvent, specifically, a lanthanum-based rare earth element-containing compound, alkylating agent and halogen It can be prepared by sequentially mixing the cargo and optionally conjugated diene-based monomers.
- the organic solvent may be a nonpolar solvent which is not reactive with the above catalyst components.
- the nonpolar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo Linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; Mixed solvents of aliphatic hydrocarbons having 5 to 20 carbon atoms such as petroleum ether, petroleum spirits, kerosene, and the like; Or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and any one or a mixture of two or more thereof may be used.
- the nonpolar solvent may be a linear, branched or cyclic aliphatic hydrocarbon or aliphatic hydrocarbon having 5 to 20 carbon atoms, and more specifically n-hexane, cyclohexane, or a mixture thereof. Can be.
- organic solvent may be appropriately selected depending on the kind of constituent materials constituting the catalyst composition, especially the alkylating agent.
- an aromatic hydrocarbon solvent may be appropriately used because it is not easily dissolved in an aliphatic hydrocarbon solvent.
- an aliphatic hydrocarbon solvent may be appropriately used.
- an aliphatic hydrocarbon solvent such as hexane which is mainly used as a polymerization solvent, it may be more advantageous for the polymerization reaction.
- the aliphatic hydrocarbon solvent can promote the catalytic activity, and by this catalytic activity can further improve the reactivity.
- the organic solvent may be used in an amount of 20 mol to 20,000 mol, and more specifically, 100 mol to 1,000 mol, based on 1 mol of the lanthanum-based rare earth element-containing compound.
- step 1 may be carried out using coordination anion polymerization, or by radical polymerization, specifically, may be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, more specifically in solution Can be summed.
- coordination anion polymerization or by radical polymerization, specifically, may be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, more specifically in solution Can be summed.
- the polymerization may be carried out by any of batch and continuous methods. Specifically, the polymerization in Step 1 may be carried out by adding a conjugated diene monomer to the catalyst composition in an organic solvent and reacting.
- the organic solvent may be added to the amount of the organic solvent that can be used to prepare the catalyst composition, the specific kind may be as described above.
- the concentration of the monomer when using the organic solvent may be 3% by weight to 80% by weight, or 10% by weight to 30% by weight.
- the polymerization may include a reaction terminator for completing a polymerization reaction such as polyoxyethylene glycol phosphate; Or additives such as antioxidants such as 2,6-di-t-butylparacresol may be used.
- additives such as chelating agents, dispersants, pH adjusting agents, deoxygenants or oxygen scavengers, which are typically used to facilitate solution polymerization, may optionally be further used.
- the polymerization may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization).
- the constant temperature polymerization refers to a polymerization method including a step of polymerizing with self-heating reaction without adding heat after the addition of the organometallic compound
- the temperature rising polymerization is a temperature by optionally applying heat after adding the organometallic compound
- the isothermal polymerization refers to a polymerization method of increasing the heat by adding heat after the addition of the organometallic compound or increasing the heat or taking away the heat to maintain a constant temperature of the polymerization product.
- the polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically, 20 ° C to 150 ° C, more specifically, to be performed for 15 minutes to 3 hours at a temperature range of 10 ° C to 120 ° C. Can be. If the temperature of the polymerization exceeds 200 °C, it is difficult to fully control the polymerization reaction, there is a fear that the cis-1,4 bond content of the resulting diene-based polymer is lowered, if the temperature is less than -20 °C polymerization reaction There is a fear that the speed and efficiency are lowered.
- Step 2 is a step of reacting the active polymer with a modifier represented by Chemical Formula 1 to prepare a modified conjugated diene-based polymer.
- the modifier represented by Formula 1 may be as described above, and may be used in the reaction by mixing one or two or more kinds.
- the modifying agent represented by Formula 1 may be used in an amount of 0.5 mol to 20 mol relative to 1 mol of the lanthanum-based rare earth element-containing compound in the catalyst composition. Specifically, the modifying agent represented by Formula 1 may be used in an amount of 1 to 10 mol based on 1 mol of the lanthanum-based rare earth element-containing compound in the catalyst composition. If the denaturant is used in an amount within the ratio range, it is possible to perform a modification reaction of optimum performance, thereby obtaining a conjugated diene polymer having a high modification rate.
- the reaction of step 2 is a modification reaction for introducing a functional group into the polymer, it may be to perform the reaction for 1 minute to 5 hours at 0 °C to 90 °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 stop 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 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 / 100g to 200 cc / 100g.
- 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 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 reinforcing performance by 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 breaking characteristics and the wet grip property.
- 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 vulcanization accelerator is not particularly limited, and specifically M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used.
- the vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.
- the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties.
- the process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel consumption) of the vulcanized rubber.
- the anti-aging agent specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone.
- the anti-aging agent may be used in an amount of 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the rubber component.
- the rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.
- a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc.
- the rubber composition may be used for 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.
- a hexane solution containing 0.23 mmol of the denaturant represented by Chemical Formula 1-1 prepared in Preparation Example 1 was added thereto, followed by a modification reaction at 70 ° C. for 30 minutes.
- hexane solution containing 1.0 g of polymerization terminator and WINGSTAY, an antioxidant 33 g of (Eliokem SAS, France) dissolved 30% by weight in hexane was added.
- the resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified butadiene polymer.
- Example 1 except that the modification reaction was carried out using the modification agent represented by Formula 1-2 prepared in Preparation Example 2 instead of the modification agent represented by Formula 1-1 prepared in Preparation Example 1
- a modified butadiene polymer was prepared in the same manner as in Example 1.
- Example 1 except that the modification reaction was carried out using the modification agent represented by Formula 1-3 prepared in Preparation Example 3 instead of the modification agent represented by Formula 1-1 prepared in Preparation Example 1
- a modified butadiene polymer was prepared in the same manner as in Example 1.
- Example 1 except that the modification reaction was carried out using the modification agent represented by Formula 1-4 prepared in Preparation Example 4 instead of the modification agent represented by Formula 1-1 prepared in Preparation Example 1
- a modified butadiene polymer was prepared in the same manner as in Example 1.
- Example 1 except that the modification was carried out using the modification agent represented by Formula 1-5 prepared in Preparation Example 5 instead of the modification agent represented by Formula 1-1 prepared in Preparation Example 1 A modified butadiene polymer was prepared in the same manner as in Example 1.
- NdV Neodymium compound 0.10 mmol hexane solution
- DIBAH diisobutylaluminum hydride
- diethylaluminum chloride diethylaluminum chloride
- BR1208 (SEETEC Co., Ltd.) was used as a comparative example as an unmodified butadiene polymer.
- CB25 (Lanxess, Inc.) was used as a comparative example as an unmodified butadiene polymer.
- Example 1 except that the modification reaction was carried out using the modification agent represented by Formula (I) prepared in Comparative Preparation Example 1 instead of the modification agent represented by Formula 1-1 prepared in Preparation Example 1 A modified butadiene polymer was prepared in the same manner as in Example 1.
- Example 1 except that the modification was carried out using the modification agent represented by Formula ii prepared in Comparative Preparation Example 2 instead of the modification agent represented by Formula 1-1 prepared in Preparation Example 1
- a modified butadiene polymer was prepared in the same manner as in Example 1.
- GPC gel permeation chromatography
- the Mooney viscosity (MV) was measured under conditions of Rotor Speed 2 ⁇ 0.02 rpm at 100 ° C. using a Large Rotor with Monsanto MV2000E. At this time, the sample used was left at room temperature (23 ⁇ 3 °C) for more than 30 minutes, and collected 27 ⁇ 3g filled inside the die cavity and operated the platen (Platen) to measure the Mooney viscosity.
- Comparative Example 1 to Example 1 to Example 5 modified butadiene polymer prepared by using an example modifier of the modifier represented by Formula 1 according to an embodiment of the present invention is not modified It was confirmed that the -S / R value of the butadiene polymer of Comparative Example 3 and the modified butadiene polymer of Comparative Examples 4 and 5 increased. This means that the modified butadiene polymer according to an embodiment of the present invention has a higher linearity than the modified or unmodified butadiene polymer of Comparative Examples 1 to 5, and as a result, a rubber prepared from a rubber composition comprising the same. It indicates that the resistance and fuel efficiency of the specimen may be excellent.
- the rubber composition is 70 parts by weight of carbon black, 100 parts by weight of each modified butadiene polymer and butadiene polymer, 22.5 parts by weight of process oil, 2 parts by weight of antioxidant (TMDQ), zinc oxide (ZnO) 3
- TMDQ antioxidant
- ZnO zinc oxide
- Each rubber composition was prepared by combining parts by weight and 2 parts by weight of stearic acid. Then, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ) and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each of the rubber compositions, and vulcanized at 160 ° C. for 25 minutes to prepare a rubber specimen.
- Tan ⁇ properties which are most important for low fuel efficiency, were measured using a Gabo DMTS 500N from Germany and measured the viscoelastic modulus (Tan ⁇ ) at 60 ° C at a frequency of 10 Hz, 3% prestrain and 3% dynamic strain.
- Tan ⁇ viscoelastic modulus
- the rubber composition comprising the modified butadiene polymer of Examples 1 to 5 prepared by using the modifier according to an embodiment of the present invention and the rubber specimen prepared therefrom are Comparative Examples 1 to The rubber composition comprising the unmodified butadiene polymer of 3 and the modified butadiene polymer of Comparative Example 4 and Comparative Example 5, respectively, and markedly improved viscoelastic properties (Tan at 60 ° C.) with improved abrasion resistance and tensile properties. Index is greatly increased by decreasing the value of ⁇ ).
- the butadiene polymer of Comparative Example 1 prepared under the same conditions as the modified butadiene polymers of Examples 1 to 5 except that the modification agent is not modified using a modifier, and commercialized and commercially available Comparative Example 2 and Comparative Example
- the butadiene polymer of 3 tensile properties were similar to those of the modified butadiene polymers of Examples 1 to 5, but the wear resistance was greatly reduced and the viscoelastic properties were significantly reduced.
- the modified butadiene polymer of Examples 1 to 5 includes an alkoxysilane group, an amine group, and an ester group, such as a modifier represented by Formula 1 according to an embodiment of the present invention, but is prepared by modifying a material having a different structure. Compared with the modified butadiene polymers of Comparative Examples 4 and 5, the wear resistance and tensile properties were excellent, and the viscoelastic properties were improved.
- the above result is equivalent to or more than that of the modified butadiene polymer of the embodiment according to an embodiment of the present invention by being modified with a specific modifier represented by the formula (1), but unmodified or similar but modified with a modifier of a different structure. It shows that it can have excellent low rotational resistance, that is, fuel economy, while having tensile properties and wear resistance.
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Abstract
Description
구분 | 실시예 | 비교예 | |||||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 | ||
DIN wt loss Index | 108 | 107 | 108 | 108 | 106 | 100 | 89 | 103 | 99 | 98 | |
인장특성 | M-300% (Index) | 109 | 108 | 108 | 106 | 107 | 100 | 95 | 103 | 101 | 102 |
인장강도(Index) | 106 | 105 | 105 | 104 | 104 | 100 | 96 | 102 | 100 | 101 | |
신율(Index) | 95 | 97 | 96 | 95 | 96 | 100 | 101 | 98 | 98 | 99 | |
Tanδ @60℃(Index) | 108 | 109 | 108 | 107 | 107 | 100 | 95 | 102 | 102 | 103 |
Claims (14)
- 청구항 1에 있어서,상기 화학식 1에서,R1, R2 및 R5는 서로 독립적으로 탄소수 1 내지 10의 알킬기로 치환되거나 비치환된 탄소수 1 내지 10의 알킬기이고,R3 및 R4는 서로 독립적으로 탄소수 1 내지 6의 알킬렌기인 것인 변성제.
- 청구항 1에 있어서,상기 변성제는 공액디엔계 중합체용 변성제인 것인 변성제.
- 청구항 5에 있어서,상기 중합체는 100,000 g/mol 내지 500,000 g/mol의 수평균분자량을 갖는 것인 변성 공액디엔계 중합체.
- 청구항 5에 있어서,상기 중합체는 분자량 분포(Mw/Mn)가 2.0 내지 3.0인 것인 변성 공액디엔계 중합체.
- 청구항 8에 있어서,상기 중합체는 100℃에서의 -S/R(stress/relaxation)의 값이 0.7 이상인 것인 변성 공액디엔계 중합체.
- 1) 탄화수소 용매 중에서, 란탄 계열 희토류 원소 함유 화합물을 포함하는 촉매 조성물 존재 하에서 공액디엔계 단량체를 중합하여 유기 금속이 결합된 활성 중합체를 제조하는 단계; 및2) 상기 활성 중합체를 하기 화학식 1로 표시되는 변성제와 반응시키는 단계를 포함하는 청구항 5에 기재된 변성 공액디엔계 중합체의 제조방법:[화학식 1]상기 화학식 1에서,R1, R2 및 R5는 서로 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기 및 탄소수 6 내지 30의 아릴기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환되거나 비치환된 탄소수 1 내지 20의 1가 탄화수소기이고,R3 및 R4는 서로 독립적으로 탄소수 1 내지 20의 선형 또는 분지형 알킬기로 치환되거나 비치환된 탄소수 1 내지 20의 2가 탄화수소기이며,n은 1 내지 3의 정수이다.
- 청구항 10에 있어서,상기 촉매 조성물은 공액디엔계 단량체 100 g을 기준으로 란탄 계열 희토류원소 함유 화합물이 0.1 mmol 내지 0.5 mmol이 되게 하는 양으로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 12에 있어서,상기 네오디뮴계 화합물은 Nd(2,2-디에틸 데카노에이트)3, Nd(2,2-디프로필 데카노에이트)3, Nd(2,2-디부틸 데카노에이트)3, Nd(2,2-디헥실 데카노에이트)3, Nd(2,2-디옥틸 데카노에이트)3, Nd(2-에틸-2-프로필 데카노에이트)3, Nd(2-에틸-2-부틸 데카노에이트)3, Nd(2-에틸-2-헥실 데카노에이트)3, Nd(2-프로필-2-부틸 데카노에이트)3, Nd(2-프로필-2-헥실 데카노에이트)3, Nd(2-프로필-2-이소프로필 데카노에이트)3, Nd(2-부틸-2-헥실 데카노에이트)3, Nd(2-헥실-2-옥틸 데카노에이트)3, Nd(2,2-디에틸 옥타노에이트)3, Nd(2,2-디프로필 옥타노에이트)3, Nd(2,2-디부틸 옥타노에이트)3, Nd(2,2-디헥실 옥타노에이트)3, Nd(2-에틸-2-프로필 옥타노에이트)3, Nd(2-에틸-2-헥실 옥타노에이트)3, Nd(2,2-디에틸 노나노에이트)3, Nd(2,2-디프로필 노나노에이트)3, Nd(2,2-디부틸 노나노에이트)3, Nd(2,2-디헥실 노나노에이트)3, Nd(2-에틸-2-프로필 노나노에이트)3 및 Nd(2-에틸-2-헥실 노나노에이트)3로 이루어진 군으로부터 선택된 1종 이상인 것인 변성 공액디엔계 중합체의 제조방법.
- 청구항 10에 있어서,상기 변성제는 란탄 계열 희토류 원소 함유 화합물 1 몰을 기준으로 0.5 몰 내지 20 몰의 비율로 사용하는 것인 변성 공액디엔계 중합체의 제조방법.
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