KR20160063980A - Modified conjugated diene polymer, method for preparing the same, and rubber composition including the same - Google Patents
Modified conjugated diene polymer, method for preparing the same, and rubber composition including the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/26—Incorporating metal atoms into the molecule
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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
- 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
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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
- C08F36/06—Butadiene
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
A tire or tire tread comprising the modified conjugated diene polymer rubber composition of claim 10.
The present invention relates to a modified conjugated diene polymer represented by the following formula (2) and a process for producing the same.
(2)
In Formula 2, R 1 , R 2 , R 3 , R 4 , P, a, b, n and 3-n are as described above.
Description
The present invention relates to a modified conjugated diene polymer, a process for producing the conjugated diene polymer, and a rubber composition containing the modified conjugated diene polymer. More particularly, the present invention relates to a modified conjugated diene polymer having excellent tensile strength, abrasion resistance, Resistant conjugated diene polymer, a process for producing the same, and a rubber composition containing the same.
The demand for stability and durability of automobiles is getting bigger and bigger. Accordingly, it is necessary to develop a rubber having a low rolling resistance, while being excellent in wet road surface resistance and mechanical strength, as a material for an automobile tire, particularly a tire tread contacting with the ground.
Conventionally, tire treads have been mixed with an inorganic filler to reinforce the above-mentioned properties in conjugated diene rubber. However, there is still room for improvement in terms of physical properties.
A problem to be solved by the present invention is to provide a modified conjugated diene polymer having excellent exothermic properties when included in a rubber composition and exhibiting tensile strength, abrasion resistance, and wet road surface resistance, and a process for producing the same.
Another object to be solved by the present invention is to provide a denaturant used in the production of the modified conjugated diene polymer.
Another object to be solved by the present invention is to provide a rubber composition excellent in pyrogenicity, tensile strength, abrasion resistance, and wet road surface resistance including the modified conjugated diene polymer, and a tire containing the rubber composition.
In order to solve such a problem,
There is provided a modified conjugated diene polymer represented by the following formula (2).
(2)
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are alkyl groups having 1 to 10 carbon atoms, P A is an integer of 0 to 2, b is an integer of 1 to 3, and n is an integer of 0 to 2;
When n is 2, two R 1 groups bonded to nitrogen may be the same or different from each other. When 3-n is 2 or more, R 2 , R 3 and R 4 may be the same or different from each other.
The present invention also relates to a process for producing an aromatic vinyl monomer, comprising the steps of: (a) polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And (b) modifying a compound represented by the following formula (1) to an active polymer having an alkali metal terminal to modify the conjugated diene polymer:
[Chemical Formula 1]
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or an alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms, and a Is an integer of 1 to 3, n is an integer of 0 to 2, and when n is 2, two R 1 bonding to nitrogen may be the same or different, and when 3-n is 2 or more, R 2 and R 3 and R < 4 > may be the same or different from each other.
The present invention also provides a modifier represented by the above formula (1).
The present invention also provides a modified conjugated diene polymer rubber composition comprising the above-mentioned modified conjugated diene polymer.
The present invention also provides a tire or tire tread comprising the modified conjugated diene polymer rubber composition.
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce a modified conjugated diene polymer exhibiting excellent exothermic properties and also exhibiting tensile strength, abrasion resistance, wet road surface resistance and the like when the silica is blended with a reinforcing agent, and can be used for a rubber composition for a tire.
Hereinafter, the present invention will be described in detail.
(A) polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And (b) modifying a compound represented by the following formula (1) to an active polymer having an alkali metal terminal to modify the conjugated diene polymer:
[Chemical Formula 1]
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or an alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms, and a Is an integer of 1 to 3, n is an integer of 0 to 2, and when n is 2, two R 1 bonding to nitrogen may be the same or different, and when 3-n is 2 or more, R 2 and R 3 and R < 4 > may be the same or different from each other.
The organic alkali metal compound is at least one compound selected from the group consisting of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert- eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium. Preferably, the organic alkali metal compound may be n-butyllithium, sec-butyllithium or a mixture thereof.
In another example, the organic alkali metal compound is selected from the group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide , And may be used in combination with other organic alkali metal compounds.
Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and the like.
Examples of the aromatic vinyl monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- 1-vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene.
The molar ratio of the organic alkali metal compound to the compound represented by the formula (1) is, for example, 1: 0.1 to 1:10, preferably 1: 0.3 to 1: 2. When the above-mentioned molar ratio satisfies this range, the conjugated diene polymer can be given an optimum performance denaturing reaction.
The active polymer having an alkali metal terminal means a polymer to which a polymeric anion and an alkali metal cation are bonded.
According to an embodiment of the present invention, the modified conjugated diene polymer may be prepared by further adding a polar additive during polymerization in the step (a). The reason why the polar additive is further added is that the polar additive controls the reaction rate of the conjugated diene monomer and the aromatic vinyl monomer.
The polar additive may be a base, or may be an ether, an amine or a mixture thereof, and specifically includes at least one of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether Diethyleneglycol, dimethylether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine And may be preferably selected from the group consisting of tetrahydropropyl propane, 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 100 g of the total amount of monomers to be added.
The polar additive may be used in an amount of 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on 1 mmol of the total amount of the organic alkali metal compound to be added.
When the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized, the block copolymer is likely to be produced largely due to the difference in the reaction rates thereof. However, when the polar additive is added, the reaction rate of the aromatic vinyl- To induce the microstructure of the corresponding copolymer, for example a random copolymer.
The polymerization of (a) may be anionic polymerization, and specifically, the polymerization of (a) may be a living anionic polymerization in which an active terminal is obtained by a growth reaction by an anion.
The polymerization of (a) may be a temperature-raising polymerization or a constant-temperature polymerization, for example.
The temperature elevation polymerization refers to a polymerization method comprising a step of increasing the reaction temperature by applying heat to the organometallic compound after the addition of the organometallic compound. The above-mentioned constant temperature polymerization means a polymerization method in which an organic metal compound is not added, .
The polymerization temperature of (a) may be -20 to 200 占 폚, 0 to 150 占 폚, or 10 to 120 占 폚, for example.
The production method of the present invention comprises (b) modifying the active polymer having an alkali metal terminal by bonding a compound represented by the following formula (1).
[Chemical Formula 1]
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or an alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms, and a Is an integer of 1 to 3, n is an integer of 0 to 2, and when n is 2, two R 1 bonding to nitrogen may be the same or different, and when 3-n is 2 or more, R 2 and R 3 and R < 4 > may be the same or different from each other.
The compound represented by the formula (1) may be a compound represented by the following formula (1a).
[Formula 1a]
The step (b) may include, for example, introducing at least one, or two or three, compounds represented by the formula (1).
The step (b) may be carried out at 0 to 90 ° C for 1 minute to 5 hours, for example.
According to one embodiment of the present invention, the method for producing the modified conjugated diene-based polymer may be, for example, a batch polymerization method (batch method) or a continuous polymerization method including one or more reactors.
Preferably, the process for producing the modified conjugated diene-based polymer of the present invention is carried out according to a continuous production process.
According to another aspect of the present invention, there is provided a modifier which is a compound represented by the following formula (1).
[Chemical Formula 1]
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or an alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms, and a Is an integer of 1 to 3, n is an integer of 0 to 2, and when n is 2, two R 1 bonding to nitrogen may be the same or different, and when 3-n is 2 or more, R 2 and R 3 and R < 4 > may be the same or different from each other.
The modifier of the present invention has a multi-functional group, which is advantageous for moon-jumping and has an advantage that physical properties can be improved when the silica is blended.
The compound represented by the formula (1) may be a compound represented by the following formula (1a).
[Formula 1a]
According to another aspect of the present invention, there is provided a modified conjugated diene polymer represented by the following formula (2).
(2)
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are alkyl groups having 1 to 10 carbon atoms, P A is an integer of 0 to 2, b is an integer of 1 to 3, and n is an integer of 0 to 2;
When n is 2, two R 1 groups bonded to nitrogen may be the same or different from each other. When 3-n is 2 or more, R 2 , R 3 and R 4 may be the same or different from each other.
The conjugated diene-based polymer chain represented by P in the above formula (2) may be, for example, a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer.
The chain composed of the conjugated dienic monomer and the aromatic vinyl monomer preferably contains 0.0001 to 40% by weight, preferably 10 to 35% by weight, based on 100% by weight of the total of the conjugated dienic monomer and the aromatic vinyl monomer, %. ≪ / RTI >
The polymer chain composed of the conjugated diene monomer and the aromatic vinyl monomer may be, for example, a random polymer chain.
The conjugated diene monomer and the aromatic vinyl monomer are as described in the above-described method for producing a modified conjugated diene polymer.
There is no particular limitation on the vinyl content of the modified conjugated diene polymer. For example, the vinyl content may be 18% or more, preferably 25% or more, and more preferably 30 to 70%. Within this range, The glass transition temperature of the tire is increased to satisfy the physical properties required for the tire such as the running resistance and the braking force when applied to the tire, and the fuel consumption is reduced.
Here, the vinyl content means the content of the vinyl group-containing monomer or the content of the 1,2-conjugated diene monomer not being 1,4-added to 100% by weight of the conjugated diene-based monomer.
The modified conjugated diene polymer may have a molecular weight distribution (Mw / Mn, PDI) of 1 to 10, preferably 1 to 5, more preferably 1 to 4. When the molecular weight distribution of the modified conjugated dienic polymer satisfies this range, excellent compatibility is achieved with the inorganic particles, so that the physical properties are improved and the workability can be greatly improved.
In particular, the modified conjugated diene polymer prepared according to the continuous production process can increase the PDI to 4.
The modified conjugated diene polymer may have a Mooney viscosity of 40 or more, preferably 40 to 100, more preferably 45 to 90. [ When the Mooney viscosity has such a range, a modified conjugated diene polymer excellent in processability, compatibility, exothermic property, tensile strength, abrasion resistance, low fuel consumption and wet road surface resistance can be produced.
The modified conjugated diene polymer may have a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 100,000 to 1,000,000 g / mol. When the number-average molecular weight of the modified conjugated diene polymer satisfies this range, the modification reaction may be most excellent or have good physical properties.
The modified conjugated diene polymer may have a vinyl content of 10% by weight or more, preferably 15% by weight or more, and more preferably 20 to 70% by weight.
The vinyl content means the content of the vinyl group-containing monomer or the content of the 1,2-conjugated diene monomer not being 1,4-added to 100% by weight of the conjugated diene-based monomer.
When the vinyl content of the modified conjugated diene polymer satisfies the above range, the glass transition temperature of the polymer is increased to satisfy the physical properties required for the tire such as the running resistance and the braking force when the tire is applied to the tire, .
According to another aspect of the present invention, there is provided a modified conjugated diene polymer rubber composition comprising 10 to 100 parts by weight of the modified conjugated diene polymer, and 0.1 to 200 parts by weight of an inorganic filler per 100 parts by weight of the modified conjugated diene polymer / RTI >
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 at least one selected from the group consisting of silica-based fillers, carbon black, and mixtures thereof. When the inorganic filler is a silica-based filler, the dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles to the ends of the modified conjugated diene polymer of the present invention.
The modified conjugated diene polymer rubber composition may further include other conjugated diene polymer.
The other conjugated diene polymer may be styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber, or a mixture thereof. The SBR may be, for example, solution styrene-butadiene rubber (SSBR).
If the other conjugated diene polymer is further included, the modified conjugated diene polymer rubber composition may include, for example, 20 to 100 parts by weight of the modified conjugated diene polymer and 0 to 80 parts by weight of the conjugated diene polymer have.
As another example, the modified conjugated diene polymer rubber composition of the present invention may comprise 20 to 99 parts by weight of the modified conjugated diene polymer and 1 to 80 parts by weight of the conjugated diene polymer.
As another example, the modified conjugated diene polymer rubber composition of the present invention comprises 10 to 100 parts by weight of the modified conjugated diene polymer, 0 to 90 parts by weight of another conjugated diene polymer, 0 to 100 parts by weight of carbon black, To 200 parts by weight of the silane coupling agent and 2 to 20 parts by weight of the silane coupling agent.
As another example, the modified conjugated diene polymer rubber composition of the present invention comprises 10 to 100 parts by weight of the modified conjugated diene polymer, 0 to 90 parts by weight of another conjugated diene polymer, 0 to 100 parts by weight of carbon black, To 200 parts by weight of the conjugated diene polymer and 2 to 20 parts by weight of the silane coupling agent. The sum of the weight of the modified conjugated diene polymer and the other conjugated diene polymer may be 100 parts by weight.
As another example, in the modified conjugated diene polymer rubber composition of the present invention, 100 parts by weight of a polymer mixture comprising 10 to 99% by weight of the modified conjugated diene polymer and 1 to 90% by weight of another conjugated diene polymer, 1 to 100 parts by weight of black, 5 to 200 parts by weight of silica and 2 to 20 parts by weight of a silane coupling agent.
The modified conjugated diene polymer rubber composition may further comprise 1 to 100 parts by weight of oil. The oil may be, for example, a mineral oil, a softener, or the like.
The oil may be used in an amount of, for example, 10 to 100 parts by weight or 20 to 80 parts by weight based on 100 parts by weight of the conjugated diene-based copolymer. The rubber composition may be softly expressed within the above range, It has excellent effect.
According to another aspect of the present invention, there is provided a tire or tire tread using the above-described modified conjugated diene polymer rubber composition.
The tire or tire tread is excellent in compatibility with an inorganic filler, and is manufactured using a rubber composition containing a modified conjugated diene polymer having improved processability, thereby exhibiting excellent heat resistance, tensile strength, abrasion resistance, wet road surface resistance, and the like But also has a low rolling resistance.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.
Example 1
270 g of styrene, 710 g of 1,3-butadiene, 5000 g of n-hexane and 0.86 g of 2,2-bis (2-oxoranyl) propane were added as a polar additive to the 20 L autoclave reactor. When the internal temperature of the reactor reached 40 占 폚, 14 mmol of n-butyllithium was charged into the reactor to conduct the adiabatic reaction. After 20 minutes, 20 g of 1,3-butadiene was added. After 5 minutes, 3.9 mmol of the compound represented by the formula (1a) was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added.
The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, followed by drying by roll to remove residual solvent and water to prepare a modified conjugated diene polymer. The analytical results of the thus-produced modified conjugated diene polymer are shown in Table 1 below.
Example 2
Three reactors were prepared. Of the three reactors, the first and second reactor were used as polymerization reactors, and the third reactor was used as a denaturing reactor. The size of the reactor is 15L, 15L and 20L, respectively.
Styrene and 1,3-butadiene diluted to a concentration of 60% by weight were charged at a rate of 314 g / h and 808 g / h, respectively, and impregnated with normal hexane at a rate of 2.6 kg / hr before entering the reactor And mixed in advance. The resultant mixed solution was continuously fed into a first-stage reactor, and then 2,2-bis (2-oxoranyl) propane diluted with 0.47 wt% as a polar additive and n-butyllithium diluted with 1 wt% Was supplied to the first reactor at a rate of 178 g / h and 37 g / h, respectively, and the internal temperature of the reactor was adjusted to 70 ° C.
The resultant polymer of the first-stage reactor was continuously supplied to the upper portion of the second-stage reactor and the polymerization reaction was carried out at a temperature of 75 ° C. The resulting polymer of the second-stage reactor was continuously fed to the upper portion of the third-stage reactor, and the compound represented by the general formula (1a) was diluted to 1% by weight and continuously supplied at a rate of 2.73 mmol / h. The polymerization reaction was stopped by adding a solution of isopropyl alcohol and an antioxidant (Wingstay-K) in a ratio of 8: 2 to the resultant polymer of the third-stage reactor at a rate of 32.5 g / h to obtain a polymer.
To 100 parts by weight of the polymer were mixed 10 phr of TDAE oil (treated distilled aromatic extract having a glass transition temperature in the range of about -44 to about -50 DEG C), and the mixture was stirred in hot water heated with steam to remove the solvent. And the solvent and water were removed by drying to obtain a modified conjugated diene polymer. The analytical results of the thus-produced modified conjugated diene polymer are shown in Table 1 below.
Example 3
The same three successive reactors as in Example 2 were used.
Styrene and 1,3-butadiene diluted to a concentration of 60% by weight were charged at a rate of 437 g / h and 692 g / h, respectively, and normal hexane was fed into the reactor at a rate of 2.6 kg / hr before removing impurities such as water, And mixed in advance. The resultant mixed solution was continuously fed into a first-stage reactor, and then 2,2-bis (2-oxoranyl) propane diluted with 0.47 wt% as a polar additive and n-butyllithium diluted with 1 wt% Was supplied to the first reactor at a rate of 74.5 g / h and 26.6 g / h, respectively, and the internal temperature of the reactor was adjusted to 70 ° C.
The resultant polymer of the first-stage reactor was continuously supplied to the upper portion of the second-stage reactor and the polymerization reaction was carried out at a temperature of 75 ° C. The resulting polymer of the second-stage reactor was continuously fed to the upper portion of the third-stage reactor, and the compound represented by the general formula (1a) was diluted to 1% by weight and continuously supplied at a rate of 2.1 mmol / h. The polymerization reaction was stopped by adding a solution of isopropyl alcohol and an antioxidant (Wingstay-K) in a ratio of 8: 2 to the resultant polymer of the third-stage reactor at a rate of 32.5 g / h to obtain a polymer.
To 100 parts by weight of the polymer were mixed 25 phr of TDAE oil (treated distilled aromatic extract having a glass transition temperature in the range of about -44 to about -50 占 폚), and the mixture was stirred in hot water heated with steam to remove the solvent. And the solvent and water were removed by drying to obtain a modified conjugated diene polymer. The analytical results of the thus-produced modified conjugated diene polymer are shown in Table 1 below.
Comparative Example One
The analytical results of the most commercially available unmodified conjugated diene polymer (5025-2HM grade, manufactured by Ransesch Germany GmbH) are shown in Table 2 below.
Comparative Example 2
The analytical results of the commercially available modified conjugated diene polymer (TUFDENETM 3835, manufactured by Asahi Kasei) are shown in Table 2 below. For reference, RAE oil was used instead of the TDAE oil used in Example 1 for the unmodified conjugated diene polymer (TUFDENETM 3835).
The analysis of the conjugated diene polymer prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was carried out by the following method.
Mooney Viscosity: 2 pieces of specimen weighing more than 15 g were preheated for one minute using MV-2000 manufactured by ALPHA Technologies and then measured at 100 ° C for 4 minutes.
B) Content of styrene monomer (SM) and vinyl (Vinyl): measured by NMR.
C) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (PDI): measured by GPC analysis under the condition of 40 캜. In this case, two columns of PLgel Olexis column manufactured by Polymer Laboratories were combined with one column of PLgel mixed-C column, and all of the new columns were of mixed bed type. Also, PS (Polystyrene) was used as a GPC reference material in molecular weight calculation.
A: 270 g of styrene, 710 g of 1,3-butadiene and 5,000 g of n-hexane
B: 314 g / h of styrene, 808 g / h of 1,3-butadiene and 2.6 kg / h of normal hexane
C: 437 g / h of styrene, 692 g / h of 1,3-butadiene and 2.6 kg / h of normal hexane
D: 5025-2HM grade, manufactured by Lanses Germany GmbH
E: TUFDENETM 3835, manufactured by Asahi Kasei
The conjugated diene polymer rubber composition was prepared by compounding A, B, C, D and E in the samples shown in Table 1 as the raw rubber in accordance with the blending conditions shown in Table 2 below. The raw materials in Table 2 are based on 100 parts by weight of rubber.
Specifically, the rubber composition of the conjugated diene polymer is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, raw material rubber (conjugated diene polymer), filler, organic silane coupling agent, oil, zincation, stearic acid antioxidant, antioxidant, wax and accelerator are kneaded using a Banbury mixer equipped with a temperature control device Respectively. At this time, the temperature of the kneader was controlled and a primary blend was obtained at an outlet temperature of 145 to 155 占 폚. In the second stage kneading, the above-mentioned primary blend was cooled to room temperature, rubber, sulfur and vulcanization accelerator were added to the kneader, and the mixture was mixed at a temperature of 100 DEG C or lower to obtain a second blend. Lastly, curing treatment was carried out at 100 占 폚 for 20 minutes to obtain the rubber compositions of Comparative Examples 1 to 2, which used the polymers of Examples 1 to 3 as raw rubber as the raw rubber, and the polymers of Comparative Examples 1 to 2 as the raw rubber To prepare a conjugated diene polymer rubber composition.
The physical properties of the rubber compositions thus prepared were measured by the following methods.
1) Tensile test
The tensile strength at the time of cutting of the test piece and the tensile stress at 300% elongation (300% modulus) were measured by the tensile test method of ASTM 412. For this purpose, Universal Testing Machine 4204 tensile tester from Instron was used. Tensile strength, modulus and elongation were measured at room temperature with a tensile speed of 50 cm / min.
2) Viscoelastic properties
A viscoelasticity tester (DMTS) from GABO Corporation was used. Tanδ was measured by varying the strain at the frequency of 10 Hz and the measurement temperature (-30 to 70 ° C) in the tensile mode.
The Pheny effect was expressed as the difference between the minimum value and the maximum value at 0.28% to 40% of the strain. The smaller the fines effect, the better the dispersibility of fillers such as silica. The low temperature 0 deg. C Tan δ is superior to the wet road surface resistance, and the lower the tan δ at 60 ° C, the less the hysteresis loss and the better the rolling resistance of the tire, that is, the low fuel consumption. Table 3 shows the physical properties of the vulcanized rubber.
(Kgf / cm2)
(Kgf / cm2)
As shown in the results of Table 3, the modified conjugated diene polymer rubber compositions of Production Examples 1 and 2 according to the present invention showed a remarkable improvement in 300% modulus (tensile stress) and tensile strength compared with Comparative Preparation Example 1 , And the value of Tan delta at 60 DEG C was low. When the modified conjugated diene polymer rubber composition of the present invention was included in the tire, the rolling resistance was lower than that of the prior art and it was confirmed that the fuel efficiency was good.
Further, in the case of the modified conjugated diene polymer rubber compositions of Production Examples 1 and 2 according to the present invention, Tan δ values at 0 ° C were similar to those of Comparative Production Example 1, and the modified conjugated diene polymer When the rubber composition was included, it was confirmed that the resistance on the wet road surface was similar to that of the rubber composition even though the rolling resistance was low.
Further, in the case of the modified conjugated diene polymer rubber compositions of Production Examples 1 and 2 according to the present invention, the ΔG 'value at 60 ° C. was significantly lower than that of Comparative Production Examples 1 and 2, there was.
In addition, even though the value of Tan δ at 0 ° C is high, the value of Tan δ at 60 ° C is low and the value of ΔG ', which is a processibility index, is low, I could confirm.
Claims (12)
(2)
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are alkyl groups having 1 to 10 carbon atoms, P A is an integer of 0 to 2, b is an integer of 1 to 3, and n is an integer of 0 to 2;
When n is 2, two R 1 groups bonded to nitrogen may be the same or different from each other. When 3-n is 2 or more, R 2 , R 3 and R 4 may be the same or different from each other.
Wherein the modified conjugated diene polymer has a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol.
(b) modifying the active polymer having an alkali metal terminal by binding a compound represented by the following formula (1) to the active polymer:
[Chemical Formula 1]
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or an alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms, and a Is an integer of 1 to 3, and n is an integer of 0 to 2;
When n is 2, two R 1 groups bonded to nitrogen may be the same or different from each other. When 3-n is 2 or more, R 2 , R 3 and R 4 may be the same or different from each other.
Wherein the compound represented by the formula (1) is a compound represented by the following formula (1a): < EMI ID =
[Formula 1a]
Wherein the molar ratio of the organic alkali metal compound to the compound represented by the formula (1) is 1: 0.1 to 1:10.
Wherein the polar additive is further added in the step (a).
Wherein the polar additive is added in an amount of 0.001 to 10 g based on 1 mmol of the total amount of the organic alkali metal compound.
[Chemical Formula 1]
Wherein R 1 is an alkyl or alkylsilyl group having 1 to 10 carbon atoms, R 2 is an alkylene group or an alkylsilylene group having 1 to 10 carbon atoms, R 3 and R 4 are an alkyl group having 1 to 10 carbon atoms, and a Is an integer of 1 to 3, and n is an integer of 0 to 2;
When n is 2, two R 1 groups bonded to nitrogen may be the same or different from each other. When 3-n is 2 or more, R 2 , R 3 and R 4 may be the same or different from each other.
Wherein the compound represented by the formula (1) is a compound represented by the following formula (1a):
[Formula 1a]
Wherein the inorganic filler is at least one member selected from the group consisting of a silica-based filler, carbon black, and mixtures thereof.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018034194A1 (en) * | 2016-08-19 | 2018-02-22 | 旭化成株式会社 | Modified conjugated diene polymer, rubber composition, and tire |
| KR20180080108A (en) * | 2017-01-03 | 2018-07-11 | 주식회사 엘지화학 | Modified cunjugated diene poylmer and rubber composition comprising the same |
| WO2021200098A1 (en) * | 2020-04-03 | 2021-10-07 | 株式会社ブリヂストン | Tire |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7531613B2 (en) | 2006-01-20 | 2009-05-12 | Momentive Performance Materials Inc. | Inorganic-organic nanocomposite |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7531613B2 (en) | 2006-01-20 | 2009-05-12 | Momentive Performance Materials Inc. | Inorganic-organic nanocomposite |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018034194A1 (en) * | 2016-08-19 | 2018-02-22 | 旭化成株式会社 | Modified conjugated diene polymer, rubber composition, and tire |
| TWI648294B (en) * | 2016-08-19 | 2019-01-21 | 日商旭化成股份有限公司 | Modified conjugated diene polymer, rubber composition, and tire |
| KR20190032437A (en) * | 2016-08-19 | 2019-03-27 | 아사히 가세이 가부시키가이샤 | Modified conjugated diene polymer, rubber composition and tire |
| JPWO2018034194A1 (en) * | 2016-08-19 | 2019-06-13 | 旭化成株式会社 | Modified conjugated diene polymer, rubber composition, and tire |
| US11414503B2 (en) | 2016-08-19 | 2022-08-16 | Asahi Kasei Kabushiki Kaisha | Modified conjugated diene-based polymer, rubber composition, and tire |
| KR20180080108A (en) * | 2017-01-03 | 2018-07-11 | 주식회사 엘지화학 | Modified cunjugated diene poylmer and rubber composition comprising the same |
| WO2021200098A1 (en) * | 2020-04-03 | 2021-10-07 | 株式会社ブリヂストン | Tire |
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