WO2015056878A1 - 말단 기능성 공액 디엔계 중합체 및 이의 제조방법 - Google Patents
말단 기능성 공액 디엔계 중합체 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2015056878A1 WO2015056878A1 PCT/KR2014/007949 KR2014007949W WO2015056878A1 WO 2015056878 A1 WO2015056878 A1 WO 2015056878A1 KR 2014007949 W KR2014007949 W KR 2014007949W WO 2015056878 A1 WO2015056878 A1 WO 2015056878A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conjugated diene
- terminal functional
- polymer
- functional conjugated
- weight
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/26—Incorporating metal 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
- C08F236/10—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Definitions
- the present invention relates to a terminal functional conjugated diene polymer and a preparation method thereof, and more particularly, to a terminal functional conjugated diene system having excellent compatibility with inorganic fillers, exothermicity, tensile strength, wear resistance, low fuel consumption, and wet road resistance. It relates to a polymer and a method for producing the same.
- the tire tread was used in combination with an inorganic filler in order to reinforce the above properties in the conjugated diene rubber, but there was a problem in that the hysteresis loss was large or the dispersibility was inferior.
- the present invention provides a terminal functional conjugated diene polymer having excellent compatibility with inorganic fillers, exothermicity, tensile strength, wear resistance, low fuel consumption and wet road resistance and a method for producing the same.
- an object of this invention is to provide the rubber composition containing the said terminal functional conjugated diene type polymer, and the tire containing this rubber composition.
- the present invention provides a terminal functional conjugated diene-based polymer, characterized in that the polymer represented by the following formula (1).
- R 1 is an alkyl group or an alkylsilyl group
- R 2 is an alkyl group or an alkylene group
- R 3 and R 4 are an alkyl group
- a is an integer from 1 to 3
- l and k are integers from 0 to 2
- m is An integer of 1 to 3
- P is a conjugated diene-based polymer chain
- A is the following Chemical Formula 2
- b is an integer of 1 to 3.
- k is 2
- Two R1 binding to nitrogen may be the same or different from each other, and corresponding groups may be the same or different when l and m are 2 or more in the same manner.
- n is 1 or 2
- R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R2 is hydrogen or an alkyl group or alkylene group having 1 to 5 carbon atoms
- D is an amine or oxygen It is a group containing.
- the present invention comprises the steps of (a) polymerizing a conjugated diene monomer or conjugated diene monomer and a vinyl aromatic monomer using an organometallic compound in a solvent to form an active polymer having a metal end;
- n is 1 or 2
- R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R2 is hydrogen or an alkyl group or alkylene group having 1 to 5 carbon atoms
- D is an amine or oxygen It is a group containing.
- R1 is an alkyl group or an alkylsilyl group
- R2 is an alkyl group or an alkylene group
- R3 and R4 are an alkyl group
- a is an integer of 1 to 3
- n is an integer of 0 to 2.
- Two R1 binding to nitrogen may be the same or different from each other, and corresponding groups may be the same or different when 3-n is 2 or more in the same manner.
- the present invention also provides a terminal functional conjugated diene-based polymer rubber composition containing 0.1 to 200 parts by weight of the inorganic filler based on 100 parts by weight of the terminal functional conjugated diene-based polymer.
- the present invention also provides a tire comprising the terminal functional conjugated diene-based polymer rubber composition.
- Terminal functional conjugated diene polymer of the present invention is characterized in that the polymer represented by the following formula (1).
- R 1 is an alkyl group or an alkylsilyl group
- R 2 is an alkyl group or an alkylene group
- R 3 and R 4 are an alkyl group
- a is an integer from 1 to 3
- l and k are integers from 0 to 2
- m is An integer of 1 to 3
- P is a conjugated diene-based polymer chain
- A is the following Chemical Formula 2
- b is an integer of 1 to 3.
- k is 2
- Two R1 binding to nitrogen may be the same or different from each other, and corresponding groups may be the same or different when l and m are 2 or more in the same manner.
- n is 1 or 2
- R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R2 is hydrogen or an alkyl group or alkylene group having 1 to 5 carbon atoms
- D is an amine or oxygen It is a group containing.
- Compound represented by the formula (2) is 4,4'-vinylidene bis (n, n-dimethylaniline) (4,4'-vinylidenebis (n, n-dimethylaniline)), 3- (2-pyrrolidino ethyl) Styrene (3- (2-Pyrrolidino Ethyl) styrene), 4- (2-pyrrolidino ethyl) styrene (4- (2-Pyrrolidino Ethyl) styrene)) and (3- (2-pyrrolidino-1- Methylethyl) -alpha-methylstyrene may be any one or more selected from the group consisting of.
- R 1 is, for example, an alkyl group or alkylsilyl group having 1 to 12 carbon atoms.
- R2 is, for example, an alkyl group or alkylene group having 1 to 12 carbon atoms.
- R3 and R4 are, for example, alkyl groups having 1 to 12 carbon atoms.
- L may be 0 or 1, for example.
- the k may be, for example, 0 or 1, and there is little hysteresis loss within this range, and there is an effect excellent in compatibility with inorganic fillers, especially silica.
- M may be 1 or 2 as an example, and may be 2 or 3 as another example.
- the total number of P may be 1 to 9, 1 to 5, or 1 to 3, and when applied to a tire within this range, it brings about an excellent wet road resistance and low fuel efficiency.
- Formula 1 may be, for example, k is 1, l is 0, m is 2.
- Chemical Formula 1 may be k is 1, l is 1, m is 1.
- the conjugated diene polymer chain may be, for example, a chain composed of a conjugated diene monomer alone or a conjugated diene monomer and a vinyl aromatic monomer.
- the conjugated diene-based polymer chain may include 0.0001 to 40% by weight of an aromatic vinyl monomer, based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer, preferably 10 to 35. It may comprise a weight percent, most preferably may be a polymer chain comprising 20 to 30% by weight.
- the polymer chain consisting of the conjugated diene monomer and the vinyl aromatic monomer may be, for example, a random polymer chain.
- the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
- the vinyl aromatic monomers are, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1 It may be one or more selected from the group consisting of -vinyl-5-hexyl naphthalene, and another example may be styrene or ⁇ -methylstyrene.
- the terminal functional conjugated diene-based polymer may be, for example, a pattern viscosity of 65 or more, or 65 to 90.
- the terminal functional conjugated diene-based polymer may have a pattern viscosity of 65 to 85, or 70 to 80.
- the terminal functional conjugated diene polymer may have a number average molecular weight of 1,000 to 2,000,000 g / mol, 10,000 to 1,000,000 g / mol, or 100,000 to 500,000 g / mol.
- the terminal functional conjugated diene polymer may have, for example, a vinyl content of 18% or more, 25% or more, preferably 30 to 70%, most preferably 40 to 60%, and within this range, the glass transition temperature of the polymer.
- a vinyl content of 18% or more, 25% or more, preferably 30 to 70%, most preferably 40 to 60%, and within this range, the glass transition temperature of the polymer.
- the vinyl content refers to the content of the monomer having a vinyl group or the content of the 1,2-added conjugated diene monomer instead of 1,4-addition based on 100% by weight of the conjugated diene monomer.
- the terminal functional conjugated diene polymer may have a molecular weight distribution (PDI) of 0.5 to 10, 0.5 to 5, or 1.0 to 2.0.
- PDI molecular weight distribution
- Method for producing a terminal functional conjugated diene polymer of the present invention (a) polymerizing a conjugated diene monomer or conjugated diene monomer and a vinyl aromatic monomer using an organometallic compound in a solvent to form an active polymer having a metal terminal ; (b) end-capping the active polymer having an alkali metal end with a compound represented by the following formula (2); And (c) it is characterized in that it comprises a step of modifying the compound represented by the formula (3) to the active polymer.
- n is 1 or 2
- R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms
- R2 is hydrogen or an alkyl group or alkylene group having 1 to 5 carbon atoms
- D is an amine or oxygen It is a group containing.
- R1 is an alkyl group or an alkylsilyl group
- R2 is an alkyl group or an alkylene group
- R3 and R4 are an alkyl group
- a is an integer of 1 to 3
- n is an integer of 0 to 2.
- Two R1 binding to nitrogen may be the same or different from each other, and corresponding groups may be the same or different when 3-n is 2 or more in the same manner.
- N may be 0 or 1, for example.
- Compound represented by the formula (2) is 4,4'-vinylidene bis (n, n-dimethylaniline) (4,4'-vinylidenebis (n, n-dimethylaniline)), 3- (2-pyrrolidino ethyl) Styrene (3- (2-Pyrrolidino Ethyl) styrene), 4- (2-pyrrolidino ethyl) styrene (4- (2-Pyrrolidino Ethyl) styrene)) and (3- (2-pyrrolidino-1- Methylethyl) -alpha-methylstyrene may be any one or more selected from the group consisting of.
- the compound represented by Chemical Formula 2 is preferably contained in 0.05 to 10% by weight based on the entire monomer.
- R1 to R4 are the same as described above.
- the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
- the vinyl aromatic monomers are, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1 It may be one or more selected from the group consisting of -vinyl-5-hexyl naphthalene, and may be styrene or ⁇ -methylstyrene as another example.
- the vinyl aromatic monomer may be 0.0001 to 40% by weight, 10 to 35% by weight or 20 to 30% by weight based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer.
- the vinyl aromatic monomer may include 0.0001 to 40% by weight of an aromatic vinyl monomer, based on a total of 100% by weight of the conjugated diene monomer and the aromatic vinyl monomer, preferably 10 to 35% by weight. And most preferably 20 to 30% by weight.
- the organometallic compound may be, for example, at least one selected from the group consisting of an organoalkali metal compound, an organolithium compound, an organosodium compound, an organopotassium compound, an organo rubidium compound, and an organo cesium compound.
- the organometallic compound may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1- 1 type selected from the group consisting of naphthyllithium, n-eicosillithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium It may be abnormal.
- the organometallic compound is n-butyllithium, sec-butyllithium or a mixture thereof.
- the organometallic compound consists of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide It may be one or more selected from the group, and may also be used in combination with other organometallic compounds.
- the organometallic compound is used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol or 0.1 to 1 mmol, based on 100 g of the total monomer.
- the molar ratio of the organometallic compound and the compound represented by Chemical Formula 3 is, for example, 1: 0.1 to 1:10, or 1: 0.5 to 1: 2.
- An active polymer having a metal end of the present invention means a polymer in which a polymer anion and a metal cation are bonded.
- a polar additive is further added during the polymerization of the above (a) to polymerize.
- the polar additive is, for example, a base, and in another example, an ether, an amine, or a mixture thereof, or tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimetal ether, Ethylene dimethyl ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethyl Selected from the group consisting of ethylenediamine, and another example is ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.
- the polar additive may be used in an amount of 0.001 to 50 g, 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 100 g of the monomer to be added.
- the polar additive may be used in an amount of 0.1 to 10 moles, 0.5 to 7 moles, or 0.5 to 4 moles based on the molar ratio of the organometallic compound introduced.
- block copolymers When copolymerizing conjugated diene-based monomers and vinyl aromatic monomers, block copolymers are generally easy to be produced due to the difference in their reaction rates.However, when the polar additive is added, the reaction rate of vinyl aromatic compounds having a slow reaction rate is increased to correspond. There is an effect of inducing a microstructure of the copolymer, for example, a random copolymer.
- the polymerization of (a) may be anionic polymerization, for example.
- the polymerization of (a) may be a living anion polymerization to obtain the active terminal by the growth reaction by the anion.
- the polymerization of (a) may be, for example, elevated temperature polymerization or constant temperature polymerization.
- the elevated temperature polymerization refers to a polymerization method including a step of raising the reaction temperature by adding heat optionally after adding the organometallic compound, and the constant temperature polymerization means a polymerization method in which no heat is optionally added after adding the organometallic compound. .
- the polymerization temperature of (a) is -20-200 degreeC, 0-150 degreeC, or 10-120 degreeC, for example.
- step (b) denaturation for example, one or more or two to three kinds of the compound represented by Chemical Formula 1 may be added.
- step (b) denaturation is to react for 1 minute to 5 hours at 0 to 90 °C, for example.
- the method for producing the terminal functional conjugated diene polymer of the present invention may be, for example, a batch process or a continuous polymerization process including one or two or more reactors.
- the terminal functional conjugated diene polymer of the present invention is characterized in that it is prepared according to the method for producing the terminal functional conjugated diene polymer, for example.
- the terminal functional conjugated diene-based polymer rubber composition of the present invention is characterized in that it comprises 0.1 to 200 parts by weight of the inorganic filler with respect to 100 parts by weight of the terminal functional conjugated diene-based polymer.
- the terminal functional conjugated diene-based polymer rubber composition may further include, for example, another terminal functional conjugated diene-based polymer.
- the other terminal functional conjugated diene polymer may be, for example, styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber, or a mixture thereof.
- SBR styrene-butadiene rubber
- BR butadiene rubber
- natural rubber or a mixture thereof.
- the SBR may be, for example, solution styrene-butadiene rubber (SSBR).
- SSBR solution styrene-butadiene rubber
- the terminal functional conjugated diene polymer rubber composition of the present invention may include, for example, 20 to 100 parts by weight of the terminal functional conjugated diene polymer and 0 to 80 parts by weight of the other terminal functional conjugated diene polymer.
- the terminal functional conjugated diene-based polymer rubber composition of the present invention may include 20 to 99 parts by weight of the terminal functional conjugated diene polymer and 1 to 80 parts by weight of the other terminal functional conjugated diene polymer.
- the terminal functional conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the terminal functional conjugated diene-based polymer, 0 to 90 parts by weight of other terminal functional conjugated diene-based polymer, 0 to 100 weight of carbon black It may be made of, including 5 to 200 parts by weight of silica and 2 to 20 parts by weight of the silane coupling agent.
- the terminal functional conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the terminal functional conjugated diene-based polymer, 0 to 90 parts by weight of other terminal functional conjugated diene-based polymer, 0 to 100 weight of carbon black Part, including 5 to 200 parts by weight of silica and 2 to 20 parts by weight of the silane coupling agent, the sum of the weights of the terminal functional conjugated diene-based polymer and other terminal functional conjugated diene-based polymer may be 100 parts by weight.
- the terminal functional conjugated diene-based polymer rubber composition of the present invention is 100 to 100 parts by weight of the polymer mixture consisting of 10 to 99% by weight of the terminal functional conjugated diene-based polymer and 1 to 90% by weight of the other terminal functional conjugated diene-based polymer 1 to 100 parts by weight of carbon black, 5 to 200 parts by weight of silica, and 2 to 20 parts by weight of a silane coupling agent.
- the inorganic filler may be, for example, 10 to 150 parts by weight, or 50 to 100 parts by weight.
- the inorganic filler may be, for example, carbon black, silica filler, or a mixture thereof.
- the inorganic filler may be silica, in which case the dispersibility is greatly improved, and the hysteresis loss is greatly reduced by the silica particles being bonded (sealed) with the ends of the terminal functional conjugated diene polymer of the present invention. It works.
- the terminal functional conjugated diene-based polymer rubber composition may further include 1 to 100 parts by weight of oil.
- the oil may be, for example, a mineral oil or a softener.
- the oil may be used in an amount of 10 to 100 parts by weight or 20 to 80 parts by weight with respect to 100 parts by weight of the conjugated diene copolymer, and exhibits good physical properties within this range, and further softens the rubber composition to have excellent processability. It works.
- the terminal functional conjugated diene-based polymer rubber composition may be used as a material of a tire or a tire tread, for example.
- the tire of the present invention is characterized in that it is produced comprising the terminal functional conjugated diene-based polymer rubber composition of the present invention.
- the denaturing agent of the present invention is characterized in that the compound represented by the following formula (3).
- R1 is an alkyl group or an alkylsilyl group
- R2 is an alkyl group or an alkylene group
- R3 and R4 are an alkyl group
- a is an integer of 1 to 3
- n is an integer of 0 to 2.
- Two R1 binding to nitrogen may be the same or different from each other, and corresponding groups may be the same or different when 3-n is 2 or more in the same manner.
- the polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual solvent and water to prepare a terminal functional conjugated diene polymer.
- the analysis results for the terminal functional conjugated diene polymer thus prepared are shown in Table 1 below.
- Example 1 Except that 1g instead of 0.5g of 3 or 4-pyrrolidinoethylstyrene in Example 1 was carried out in the same manner as in Example 1, to prepare a terminal functional conjugated diene-based polymer.
- the analysis results for the terminal functional conjugated diene polymer thus prepared are shown in Table 1 below.
- Example 1 In Example 1, except that 1g of (3- (2-pyrrolidino-1-methylethyl) -alpha-methylstyrene was added instead of 3 or 4-pyrrolidinoethylstyrene.
- the analysis results of the terminal functional conjugated diene polymer thus prepared are shown in Table 1 below.
- a terminal functional conjugated diene-based polymer was prepared in the same manner as in Example 1, except that Bis (methyldiethoxysilylpropyl) -N-methylamine was not added in Example 1.
- the analysis results for the terminal functional conjugated diene polymer thus prepared are shown in Table 1 below.
- Example 1 In Example 1, except that 3 or 4-pyrrolidinoethylstyrene was added together with styrene and butadiene without adding bis (methyldiethoxysilylpropyl) -N-methylamine. In this way, a random functional conjugated diene polymer was prepared.
- the analysis results for the random functional conjugated diene polymer thus prepared are shown in Table 1 below.
- Example 1 Except that 3 or 4-pyrrolidinoethyl styrene in Example 1 was carried out in the same manner as in Example 1, to prepare a terminal functional conjugated diene polymer.
- Pattern Viscosity After preheating for 1 minute using two or more 15g weight of the specimen using MV-2000 of ALPHA Technologies Inc. was measured for 4 minutes at 100 °C.
- the column was a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories, and all of the newly replaced columns were mixed bed type columns.
- polystyrene (PS) was used as a GPC standard material for molecular weight calculation.
- Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1 were used as raw material rubbers, and blended under the compounding conditions shown in Table 2 to provide terminal functional conjugated diene-based polymer rubber compositions in Examples 4 to 6 and Prepared in Comparative Examples 4-6.
- a raw material rubber (terminal functional conjugated diene polymer), a filler, Organosilane coupling agents, oils, zincated, stearic acid antioxidants, antioxidants, waxes and accelerators were kneaded.
- the temperature of the kneader was controlled and the primary blend was obtained at the discharge temperature of 140-150 degreeC.
- rubber, sulfur and a vulcanization accelerator were added to the kneader to obtain a secondary blend at a discharge temperature of 45 to 60 ° C.
- a secondary blend was molded as a kneading in the third stage, and vulcanized by vulcanization press at 180 ° C. for T90 + 10 minutes to prepare a vulcanized rubber.
- Tan ⁇ was measured by changing the strain at a frequency of 10 Hz and each measurement temperature (0 to 60 ° C.) in a torsion mode, and Comparative Example 1 was expressed as an index by 100. The higher the low temperature 0 ° C Tan ⁇ and the lower the high temperature 60 ° C Tan ⁇ , the larger the index was used as an indicator of the improvement of physical properties.
- the index value of Tan ⁇ at 60 ° C. was also higher than that of Comparative Examples 4 to 6, so that the terminal functional conjugate of the present invention was applied to the tire.
- the diene-based polymer is included, it was confirmed that the rolling resistance has a lower value than the prior art.
- Example 5 the Tan ⁇ value at 60 ° C. was higher than that of Example 4 as the content of the modified monomer was increased, so that the effect of the monomer could be clearly confirmed.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
실시예1 | 실시예2 | 실시예3 | 비교예1 | 비교예2 | 비교예3 | ||
시료 | A | B | C | D | E | F | |
변성모노머 | 종류 | a | a | b | a | a | - |
함량(wt%) | 0.5 | 1 | 1 | 0.5 | - | ||
변성제 | 가 | 가 | 가 | - | 가 | 가 | |
무니 | 74 | 74 | 75 | 63 | 74 | ||
Tg(℃) | -25.4 | -25.2 | -25.4 | -24.3 | -26.3 | -25.4 | |
스타이렌(%) | 27 | 27 | 27 | 27 | 26 | 27 | |
비닐(%) | 42 | 41 | 42 | 40 | 43 | 42 | |
GPC(×104) | Mn | 36 | 35 | 36 | 34 | 37 | 36 |
Mw | 48 | 46 | 50 | 42 | 51 | 47 | |
PDI | 1.3 | 1.3 | 1.4 | 1.2 | 1.4 | 1.3 |
(단위: 중량부) | S-1 |
고무 | 100.0 |
실리카 | 70.0 |
커플링제 | 11.02 |
오일 | 33.75 |
아연화 | 3.0 |
스테아르산 | 2.0 |
산 d아지제 | 2.0 |
노화방지제 | 2.0 |
왁스 | 1.0 |
고무촉진제 | 1.75 |
황 | 1.5 |
가황촉진제 | 2.0 |
총중량 | 230.2 |
구분 | 실시예4 | 실시예5 | 실시예6 | 비교예4 | 비교예5 | 6비교예 |
시료 | A | B | C | D | E | F |
300%모듈러스(kgf/cm2) | 124 | 128 | 130 | 122 | 118 | 121 |
인장강도(kgf/cm2) | 183 | 185 | 181 | 192 | 185 | 168 |
Tan δat 0℃ | 111 | 111 | 114 | 100 | 100 | 110 |
Tan δat 60℃ | 107 | 108 | 106 | 100 | 93 | 103 |
Claims (23)
- 하기 화학식 1로 표시되는 중합체인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.[화학식 1](상기 식에서, R1은 알킬기 또는 알킬실릴기이고, R2는 알킬기 또는 알킬렌기이고, R3 및 R4는 알킬기이며, a는 1 내지 3의 정수이고, l 및 k는 0 내지 2의 정수이며, m은 1 내지 3의 정수이고, l+k+m은 3을 만족하며, P는 공액 디엔계 폴리머 사슬이고, A는 하기 화학식 2이고, b는 1 내지 3의 정수이다. 또한, k가 2인 경우 질소에 결합하는 두 개의 R1은 서로 동일하거나 다를 수 있고, 동일한 방식으로 l과 m이 2 이상인 경우에 그에 해당하는 기들(groups)은 서로 동일하거나 다를 수 있다.)[화학식 2](상기 식에서, n 은 1 또는 2이며, R1은 수소, 또는 탄소의 개수가 1~5개인 알킬기, R2는 수소, 또는 탄소의 개수가 1~5개인 알킬기 또는 알킬렌기이며, D는 아민 또는 산소를 함유한 기이다.)
- 청구항 1에 있어서,상기 화학식 2는 4,4'-비닐리덴 비스(n,n-디메틸아닐린) (4,4'-vinylidenebis(n,n-dimethylaniline)), 3-(2-피롤리디노 에틸)스티렌 (3-(2-Pyrrolidino Ethyl)styrene)), 4-(2-피롤리디노 에틸)스티렌 (4-(2-Pyrrolidino Ethyl)styrene)) 및 (3-(2-피롤리디노-1-메틸에틸)-알파-메틸스티렌으로 이루어지는 군에서 선택되는 어느 하나 이상 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 l은, 0 또는 1인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 k는, 0 또는 1인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 화학식 1은, k가 1이고, l이 1이며, m이 1인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 공액 디엔계 폴리머 사슬은, 공액 디엔 단량체 및 비닐 방향족 단량체를 포함하여 이루어진 랜덤 공중합체 사슬인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 말단 기능성 공액 디엔계 중합체는, 수평균분자량이 1,000 내지 2,000,000 g/mol인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 말단 기능성 공액 디엔계 중합체는, 비닐 함량이 18% 이상인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 말단 기능성 공액 디엔계 중합체는, 공액디엔계 단량체와 방향족 비닐계 단량체를 합한 총 100 중량%를 기준으로 방향족 비닐계 단량체가 10 내지 40 중량%로 포함된 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 말단 기능성 공액 디엔계 중합체는, 무늬점도가 65 이상인 것을 특징으로 하는 변성 공액디엔계 중합체.
- (a) 공액 디엔계 단량체 또는 공액 디엔계 단량체와 비닐 방향족 단량체를 용매 하에서 유기금속 화합물을 이용하여 중합시켜 금속 말단을 갖는 활성 중합체를 형성하는 단계;(b) 알칼리 금속 말단을 갖는 활성 중합체를 하기 화학식 2로 표시되는 화합물로 엔드-캡핑(end-capping) 시키는 단계; 및(c) 상기 활성 중합체에 하기 화학식 3으로 표시되는 화합물을 투입하여 변성시키는 단계;를 포함하는 말단 기능성 공액 디엔계 중합체의 제조방법.[화학식 2](상기 식에서, n 은 1 또는 2이며, R1은 수소, 또는 탄소의 개수가 1~5개인 알킬기, R2는 수소, 또는 탄소의 개수가 1~5개인 알킬기 또는 알킬렌기이며, D는 아민 또는 산소를 함유한 기이다.)[화학식 3](R1은 알킬기 또는 알킬실릴기이고, R2는 알킬기 또는 알킬렌기이며, R3 및 R4는 알킬기이고, a는 1 내지 3의 정수이고, n은 0 내지 2의 정수이다. 또한, n이 2인 경우 질소에 결합하는 두 개의 R1은 서로 동일하거나 다를 수 있고, 동일한 방식으로 3-n이 2 이상인 경우에 그에 해당하는 기들(groups)은 서로 동일하거나 다를 수 있다.)
- 청구항 11에 있어서,상기 화학식 2는 4,4'-비닐리덴 비스(n,n-디메틸아닐린) (4,4'-vinylidenebis(n,n-dimethylaniline)), 3-(2-피롤리디노 에틸)스티렌 (3-(2-Pyrrolidino Ethyl)styrene)), 4-(2-피롤리디노 에틸)스티렌 (4-(2-Pyrrolidino Ethyl)styrene)) 및 (3-(2-피롤리디노-1-메틸에틸)-알파-메틸스티렌으로 이루어지는 군에서 선택되는 어느 하나 이상 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 화학식 2로 표시되는 화합물은, 단량체 전체를 기준으로 0.05중량% 내지 10중량%로 포함되는 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 유기금속 화합물은, 유기 알칼리 금속 화합물인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 유기금속 화합물은, 상기 단량체 총 100 g을 기준으로 0.01 내지 10 mmol로 사용되는 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 유기금속 화합물과 상기 화학식 3으로 표시되는 화합물의 몰비는, 1: 0.1 내지 1: 10인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 (a)의 중합은, 극성첨가제가 더 투입되는 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 17에 있어서,상기 극성첨가제는, 상기 유기금속 화합물 총 1 mmol을 기준으로 0.1 내지 10 몰비로 투입되는 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체의 제조방법.
- 청구항 11 내지 청구항 18 중 어느 한 항의 말단 기능성 공액 디엔계 중합체의 제조방법에 따라 제조된 말단 기능성 공액 디엔계 중합체.
- 청구항 1 내지 청구항 10 중 어느 한 항의 말단 기능성 공액 디엔계 중합체 100 중량부에 대하여 무기 충진제 0.1 내지 200 중량부를 포함하여 이루어지는 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체 고무 조성물.
- 청구항 20에 있어서,상기 변성 공액디엔계 중합체 10 내지 100 중량%와 이와 다른 말단 기능성 공액 디엔계 중합체 0 내지 90 중량%로 이루어진 중합체 혼합물 100 중량부에 카본블랙 0 내지 100 중량부, 실리카 5 내지 200 중량부 및 실란 커플링제 2 내지 20 중량부를 포함하여 이루어지는 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체 고무 조성물.
- 청구항 20에 있어서,상기 무기 충진제는, 실리카계 충진제인 것을 특징으로 하는 말단 기능성 공액 디엔계 중합체 고무 조성물.
- 청구항 20의 말단 기능성 공액 디엔계 중합체 고무 조성물을 포함하여 이루어진 타이어.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/911,993 US10030079B2 (en) | 2013-10-17 | 2014-08-26 | End-functional conjugated diene-based polymer and manufacturing method therefor |
JP2016533259A JP6312173B2 (ja) | 2013-10-17 | 2014-08-26 | 末端機能性共役ジエン系重合体及びこの製造方法 |
CN201480048059.6A CN105612184B (zh) | 2013-10-17 | 2014-08-26 | 末端官能化的基于共轭二烯的聚合物及其制造方法 |
EP14853538.8A EP3059259B1 (en) | 2013-10-17 | 2014-08-26 | End-functional conjugated diene-based polymer and manufacturing method therefor |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20130124074 | 2013-10-17 | ||
KR10-2013-0124074 | 2013-10-17 | ||
KR20140085290A KR101508465B1 (ko) | 2013-10-17 | 2014-07-08 | 말단 기능성 공액 디엔계 중합체 및 이의 제조방법 |
KR10-2014-0085290 | 2014-07-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015056878A1 true WO2015056878A1 (ko) | 2015-04-23 |
Family
ID=52828286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2014/007949 WO2015056878A1 (ko) | 2013-10-17 | 2014-08-26 | 말단 기능성 공액 디엔계 중합체 및 이의 제조방법 |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2015056878A1 (ko) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018088710A1 (ko) * | 2016-11-14 | 2018-05-17 | 주식회사 엘지화학 | 변성 단량체, 이를 포함하는 변성 공액디엔계 중합체 및 이의 제조방법 |
US10662143B2 (en) | 2016-11-14 | 2020-05-26 | Lg Chem, Ltd. | Modification monomer, modified conjugated diene-based polymer including the same and method for preparing the polymer |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4935471A (en) * | 1987-10-15 | 1990-06-19 | The Goodyear Tire & Rubber Company | Capped polydienes |
KR20030060752A (ko) | 2002-01-09 | 2003-07-16 | 스미또모 가가꾸 고교 가부시끼가이샤 | 개질 중합체 고무의 제조방법 |
EP1714984A1 (en) * | 2005-04-20 | 2006-10-25 | The Goodyear Tire & Rubber Company | Rubber composition containing an alkoxysilane coupled in-chain functionalized elastomer and tire with component thereof |
JP2010116546A (ja) * | 2008-10-16 | 2010-05-27 | Sumitomo Rubber Ind Ltd | ゴム組成物及びタイヤ |
KR20130018729A (ko) * | 2010-03-31 | 2013-02-25 | 제이에스알 가부시끼가이샤 | 변성 공액 디엔계 고무의 제조 방법, 변성 공액 디엔계 고무, 및 고무 조성물 |
KR20130090811A (ko) * | 2012-02-06 | 2013-08-14 | 주식회사 엘지화학 | 변성 공액 디엔계 중합체 및 이의 제조방법 |
-
2014
- 2014-08-26 WO PCT/KR2014/007949 patent/WO2015056878A1/ko active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4935471A (en) * | 1987-10-15 | 1990-06-19 | The Goodyear Tire & Rubber Company | Capped polydienes |
KR20030060752A (ko) | 2002-01-09 | 2003-07-16 | 스미또모 가가꾸 고교 가부시끼가이샤 | 개질 중합체 고무의 제조방법 |
EP1714984A1 (en) * | 2005-04-20 | 2006-10-25 | The Goodyear Tire & Rubber Company | Rubber composition containing an alkoxysilane coupled in-chain functionalized elastomer and tire with component thereof |
JP2010116546A (ja) * | 2008-10-16 | 2010-05-27 | Sumitomo Rubber Ind Ltd | ゴム組成物及びタイヤ |
KR20130018729A (ko) * | 2010-03-31 | 2013-02-25 | 제이에스알 가부시끼가이샤 | 변성 공액 디엔계 고무의 제조 방법, 변성 공액 디엔계 고무, 및 고무 조성물 |
KR20130090811A (ko) * | 2012-02-06 | 2013-08-14 | 주식회사 엘지화학 | 변성 공액 디엔계 중합체 및 이의 제조방법 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018088710A1 (ko) * | 2016-11-14 | 2018-05-17 | 주식회사 엘지화학 | 변성 단량체, 이를 포함하는 변성 공액디엔계 중합체 및 이의 제조방법 |
US10662143B2 (en) | 2016-11-14 | 2020-05-26 | Lg Chem, Ltd. | Modification monomer, modified conjugated diene-based polymer including the same and method for preparing the polymer |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2013119006A1 (ko) | 변성 공액 디엔계 중합체 및 이의 제조방법 | |
WO2015016405A1 (ko) | 변성 공액 디엔계 중합체 및 이의 제조방법 | |
WO2015056898A1 (ko) | 변성 공액 디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 | |
WO2014175561A1 (ko) | 공역디엔계 중합체의 제조방법, 상기 중합체를 포함하는 조성물 및 상기 조성물을 포함하는 타이어 | |
KR101594217B1 (ko) | 변성 공액 디엔계 중합체의 연속 제조방법, 이로부터 수득된 중합체 및 이를 포함하는 고무 조성물 | |
WO2018030645A1 (ko) | 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 | |
WO2016072584A1 (ko) | 아스팔트 개질제 및 이를 포함하는 아스팔트 조성물 | |
WO2015034110A1 (ko) | 변성 공액 디엔계 중합체, 그의 제조방법 및 상기 변성 공액 디엔계 중합체를 포함하는 고무 조성물 | |
WO2015194786A1 (ko) | 변성 공액 디엔계 중합체, 이를 포함하는 변성 고무 조성물 및 변성 공액 디엔계 중합체의 제조방법 | |
WO2015056994A1 (ko) | 말단 기능성 공액 디엔계 중합체 및 이의 제조방법 | |
WO2014175562A1 (ko) | 변성 공액 디엔계 중합체의 연속 제조방법, 이로부터 수득된 중합체 및 이를 포함하는 고무 조성물 | |
WO2016104987A1 (ko) | 변성 공액디엔계 중합체 및 그를 포함하는 조성물 | |
WO2016093496A1 (ko) | 변성 공역디엔계 중합체, 이를 포함하는 변성 고무 조성물 및 변성 공역디엔계 중합체의 제조방법 | |
KR20130090810A (ko) | 변성 공액 디엔계 중합체 및 이의 제조방법 | |
WO2016204575A1 (ko) | 관능기가 도입된 아미노실란계 말단변성제를 이용하는 고무 조성물의 제조방법 및 이에 따라 제조한 고무 조성물 | |
WO2017191921A1 (ko) | 변성제 및 이를 이용하여 제조된 변성 공액디엔계 중합체 | |
WO2018074662A1 (ko) | 아스팔트 개질제 및 이를 포함하는 아스팔트 조성물 | |
WO2017111487A1 (ko) | 변성 공액디엔계 중합체 및 이의 제조방법 | |
WO2015057021A1 (ko) | 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 | |
WO2016089035A1 (ko) | 아민기를 포함하는 음이온 말단을 갖는 음이온 중합 개시제, 이를 이용한 변성 공역디엔계 공중합체의 제조방법, 및 이에 따라 제조한 변성 공역디엔계 공중합체를 포함하는 고무 조성물 | |
WO2016111445A1 (ko) | 변성 공역디엔계 중합체, 이를 포함하는 변성 고무 조성물 및 변성 공역디엔계 중합체의 제조방법 | |
WO2017150852A1 (ko) | 아자실란계 변성제 및 이를 이용한 변성 공액디엔계 중합체의 제조방법 | |
WO2017061831A1 (ko) | 변성 공액디엔계 중합체, 이의 제조방법 및 이를 포함하는 고무 조성물 | |
WO2017188641A2 (ko) | 변성 공액디엔계 중합체 및 이의 제조방법 | |
WO2018128330A1 (ko) | 아민 화합물, 이로부터 유래된 작용기를 포함하는 변성 공액디엔계 중합체 및 변성 공액디엔계 중합체의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14853538 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016533259 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2014853538 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014853538 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14911993 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |