KR102019840B1 - Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer - Google Patents
Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer Download PDFInfo
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- KR102019840B1 KR102019840B1 KR1020150184235A KR20150184235A KR102019840B1 KR 102019840 B1 KR102019840 B1 KR 102019840B1 KR 1020150184235 A KR1020150184235 A KR 1020150184235A KR 20150184235 A KR20150184235 A KR 20150184235A KR 102019840 B1 KR102019840 B1 KR 102019840B1
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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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- 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
- C08C19/22—Incorporating nitrogen 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-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
- 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
Abstract
The present invention provides a rubber modifier, a modified conjugated diene-based polymer comprising a functional group derived from the modifier, a method for producing a modified conjugated diene-based polymer using the modifier, a rubber composition comprising the modified conjugated diene-based polymer, and a rubber composition prepared from the rubber composition. It's about tires. Accordingly, the modifier may be used as a modifier of the conjugated diene-based polymer to bind to the conjugated diene-based polymer chain to easily introduce a filler affinity functional group. Therefore, the modified conjugated diene-based polymer prepared using the rubber modifier compound may have excellent affinity with the filler, and as a result, the processed article (eg, tire) manufactured from the rubber composition including the polymer may have a tensile strength, Abrasion resistance and wet road resistance properties may be excellent.
Description
The present invention provides a rubber modifier, a modified conjugated diene-based polymer comprising a functional group derived from the modifier, a method for producing a modified conjugated diene-based polymer using the modifier, a rubber composition comprising the modified conjugated diene-based polymer, and a rubber composition prepared from the rubber composition. It's about tires.
In recent years, with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low rolling resistance, excellent wear resistance and tensile properties, and adjusting stability represented by wet skid resistance.
In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, a repulsive elasticity of 50 ° C to 80 ° C, Tan δ, and the like are used. That is, a rubber material having a high resilience at the above temperature or a small Tan δ is preferable.
As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low wet skid resistance. Recently, 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. . Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR rubber, and the movement of the chain ends can be reduced by the binding or modification of the chain ends, and the bonding strength with fillers such as silica or carbon black can be increased. It is widely used as a rubber material for tires.
When the solution-polymerized SBR is used as a rubber material for tires, the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby controlling tire required properties such as running resistance and braking force, and properly adjusting the glass transition temperature. By adjusting the fuel consumption can be reduced.
The solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers.
For example, US Pat. No. 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, a monofunctional initiator, using a binder such as a tin compound. It was.
Meanwhile, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as reinforcing fillers, low hysteresis loss and wet skid resistance are improved. However, the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler may be used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent.
Thus, a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal portion, but the effect is not sufficient.
Therefore, there is a need for development of a rubber having high affinity with fillers including silica.
The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a modifier represented by the formula (1) which can provide a filler, in particular a silica-based filler affinity functional group.
Another object of the present invention is to provide a modified conjugated diene-based polymer comprising the functional group derived from the rubber modifier.
Another object of the present invention to provide a method for producing a modified conjugated diene polymer using the compound for the rubber modifier.
In addition, another object of the present invention to provide a rubber composition comprising the modified conjugated diene-based polymer.
Furthermore, another object of the present invention is to provide a tire made from the rubber composition.
In order to solve the above problems, a modifier represented by the following formula (1) is provided.
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
In addition, the present invention provides a modified conjugated diene-based polymer comprising a compound derived unit represented by the following formula (1).
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
In addition, the present invention is to prepare an active polymer in which the alkali metal is bonded to at least one terminal by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal 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 the compound represented by the formula (1).
Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a tire made from the rubber composition.
The modifier represented by the formula (1) according to the present invention can be used as a modifier for rubber, in particular conjugated diene-based polymer, it is coupled to the conjugated diene-based polymer chain can easily introduce a filler affinity functional group.
In addition, the modified conjugated diene-based polymer according to the present invention may be excellent in affinity with the filler, in particular, silica-based filler by binding a functional group, such as a siloxane group and an amine group represented by the formula (1) in the polymer chain.
In addition, the production method according to the present invention can easily prepare a modified conjugated diene-based polymer having excellent modification rate by using the compound represented by the formula (1).
Furthermore, the rubber composition according to the present invention may have excellent processability by including a modified conjugated diene-based polymer having excellent affinity with the filler, and as a result, the processed product (eg, a tire) manufactured using the rubber composition may be Tensile strength, wear resistance and wet road resistance properties may be excellent.
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
The present invention provides a modifier that can provide an affinity functional group with reinforcing fillers, especially silica based fillers.
The denaturing agent according to an embodiment of the present invention is characterized by represented by the following formula (1).
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
Specifically, in Formula 1, A and B are independently an alkylene group having 1 to 6 carbon atoms, R 2 , R 3 , R 5 and R 6 are independently alkyl having 1 to 10 carbon atoms, and R 1 and R 4 is independently from each other —COR 7 or —COR 7 R 8 , wherein C may be an alkylene having 1 to 6 carbon atoms.
In Formula 1, Q is -CSiR 9 R 10 R 11, wherein C is alkylene having 1 to 6 carbon atoms, and R 9 , R 10 and R 11 may be independently alkoxy groups having 1 to 3 carbon atoms. have.
More specifically, Formula 1 may be a modifier represented by the following Formula 2 or Formula 3.
[Formula 2]
[Formula 3]
In addition, the modifier represented by Formula 1 may be a modifier for a conjugated diene polymer. Herein, the conjugated diene polymer may be a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
In addition, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
The modified conjugated diene-based polymer according to an embodiment of the present invention may include a modifier-derived functional group represented by the formula (1). That is, the modified conjugated diene-based polymer may be modified by a modifier represented by Formula (1).
The modified conjugated diene-based polymer has a siloxane group and an amine group bonded to the polymer chain may be excellent in affinity with the filler, in particular silica filler. Accordingly, the physical properties of the rubber composition including the modified conjugated diene-based polymer may be excellent, and consequently, the tensile strength of a molded article, such as a tire, manufactured using the rubber composition may be excellent. Abrasion resistance and wet road resistance can be improved.
Specifically, the modifier represented by Formula 1 may be as described above.
On the other hand, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a homopolymer or a copolymer, it may be prepared by the manufacturing method described below.
Specifically, when the modified conjugated diene-based polymer is a homopolymer, it may be a modified conjugated diene polymer, and when the modified conjugated diene-based polymer is a copolymer, the modified conjugated diene-based polymer is a conjugated diene monomer-derived unit and an aromatic vinyl monomer. It may include a derived unit. In addition, when the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer.
Here, the "random copolymer" may indicate that the structural units constituting the copolymer are randomly arranged.
In addition, the modified conjugated diene-based polymer may have a number average molecular weight of 1,000 g / mol to 2,000,000 g / mol, specifically 10,000 g / mol to 1,000,000 g / mol. More specifically, it may be from 100,000 g / mol to 1,000,000 g / mol.
The modified conjugated diene-based polymer may have a weight average molecular weight of 10,000 g / mol to 3,000,000 g / mol, specifically may be 100,000 g / mol to 2,000,000 g / mol.
The modified conjugated diene-based polymer may be a polydispersity index of 0.5 to 10, specifically, 0.5 to 5.
In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 5% by weight to 50% by weight. When the vinyl content is in the above range, the glass transition temperature can be adjusted to an appropriate range, and when applied to a tire, not only the properties required for the tire such as running resistance and braking force are excellent, but also the fuel consumption is reduced.
In this case, the vinyl content represents the content of the 1,2-added conjugated diene monomer instead of 1,4-addition based on 100% by weight of the conjugated diene polymer composed of a monomer having a vinyl group or a conjugated diene monomer.
In addition, the modified conjugated diene-based polymer has a characteristic of viscoelasticity, when measured at 10 Hz through DMA after silica blending, the Tan δ value (Tanδ at 0 ° C.) at 0 ° C. may be 0.4 to 1, and specifically, It may be from 0.5 to 1. If the above range is indicated, road surface resistance or wetting resistance may be significantly improved as compared with a conventional conjugated diene-based polymer.
In addition, the Tan δ value (Tan δ at 60 ° C.) at 60 ° C. may be 0.3 to 0.2 or 0.15 to 0.1. If the above range is indicated, the running resistance or rotational resistance (RR) can be significantly improved compared to the conventional conjugated diene-based polymer.
In addition, the present invention provides a method for producing a modified conjugated diene-based polymer using a modifier represented by the formula (1).
The production method according to an embodiment of the present invention is an active polymer in which an alkali metal is bonded to at least one terminal by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. Preparing (step 1); And reacting the active polymer with the denaturant represented by Chemical Formula 1 (step 2).
Step 1 is a step for preparing an active polymer having an alkali metal bonded to at least one end thereof, and is performed by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. Can be.
The polymerization of step 1 may be to use a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer together as a monomer. That is, the polymer prepared by the above production method according to an embodiment of the present invention may be a homopolymer derived from a conjugated diene monomer or a copolymer derived from a conjugated diene monomer and an aromatic vinyl monomer.
The conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.
When the conjugated diene-based monomer and the aromatic vinyl monomer are used together as the monomer, the conjugated diene-based monomer may be 50 wt% or more, specifically, in the finally prepared modified conjugated diene-based polymer. It may be used in an amount comprised from 50% to 95% by weight, more specifically from 60% to 95% by weight.
The aromatic vinyl monomer is not particularly limited, but for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p It may be one or more selected from the group consisting of -methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.
When the conjugated diene monomer and the aromatic vinyl monomer are used together as the monomer, the aromatic vinyl monomer may have 50% by weight or less of the unit derived from the aromatic vinyl monomer in the finally prepared modified conjugated diene polymer. 5 wt% to 50 wt%, more specifically 5 wt% to 40 wt% may be used.
Herein, the "derived unit" may refer to a component, a structure, or the substance itself resulting from a substance.
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 organoalkali metal compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of monomers, and specifically, in an amount of 0.05 mmol to 5 mmol, based on 100 g of monomers.
The organoalkali metal compound is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, Phenyllithium, 1-naphthyllithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naph One or more selected from the group consisting of sodium sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropylamide Can be.
The polymerization of step 1 may be performed by further adding a polar additive as needed, the polar additive may be added to 0.001 parts by weight to 10 parts by weight based on 100 parts by weight of the total monomer. Specifically, the amount may be added in an amount of 0.001 part by weight to 1 part by weight, more specifically 0.001 part by weight to 0.5 part by weight based on 100 parts by weight of the total monomer.
The polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis It may be one or more selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.
In the manufacturing method according to an embodiment of the present invention, when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, the reaction rate can be easily compensated for by forming a random copolymer. Can be induced.
The polymerization of step 1 may be carried out through adiabatic polymerization, or isothermal polymerization.
Here, adiabatic polymerization refers to a polymerization method including a step of polymerizing with self-heating reaction without adding heat after the addition of the organoalkali metal compound, and the isothermal polymerization is an arbitrary heat after adding the organoalkali metal compound. It represents a polymerization method for maintaining a constant temperature of the polymer by adding or taking away heat.
The polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically 0 ° C to 150 ° C, and more specifically 10 ° C to 120 ° C.
Step 2 is a step of reacting the active polymer with a compound represented by Formula 1 to prepare a modified conjugated diene-based polymer.
In this case, the compound represented by Chemical Formula 1 may be as described above.
The compound represented by Chemical Formula 1 may be used in a ratio of 0.1 mol to 10 mol with respect to 1 mol of the organic alkali metal compound. Specifically, the compound represented by Formula 1 may be used in 0.3 mol to 2 mol compared to 1 mol of the organic alkali metal compound. If the compound represented by Chemical Formula 1 is used in the above ratio, the denaturation reaction may be effectively performed.
The reaction of step 2 according to an embodiment of the present invention is a modification reaction for introducing a functional group into the polymer, each reaction may be performed for 1 minute to 5 hours in the temperature range of 10 ℃ to 90 ℃.
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.
In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
The rubber composition according to an embodiment of the present invention may be a modified conjugated diene-based polymer containing 10 wt% or more, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt%. have. If the content of the modified conjugated diene-based polymer is less than 10% by weight, the effect of improving the wear resistance and crack resistance of a molded article, for example, a tire manufactured using the rubber composition may be insignificant.
In addition, 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.
Specifically, the rubber composition may include 20 parts by weight to 100 parts by weight of the modified conjugated diene-based polymer and 0 parts by weight to 80 parts by weight of other rubber components based on 100 parts by weight of the rubber composition.
In addition, the rubber composition according to another embodiment of the present invention is 10 parts by weight to 100 parts by weight of the modified conjugated diene-based polymer, 0 parts by weight to 90 parts by weight of other rubber components, 0 parts by weight to 100 parts by weight of carbon black, 5 parts by weight to 200 parts by weight of silica and 2 parts by weight to 20 parts by weight of the silane coupling agent, wherein the parts by weight are based on 100 parts by weight of the total amount of the modified conjugated diene-based polymer and other rubber components. Can be.
In addition, the rubber composition according to another embodiment of the present invention comprises 10% to 99% by weight of the modified conjugated diene-based polymer and 1% to 90% by weight of the other rubber component, the modified conjugated diene-based polymer And about 1 part by weight to 100 parts by weight of carbon black, about 5 parts by weight to about 200 parts by weight of silica, and about 2 parts by weight to about 20 parts by weight of the silane coupling agent, based on 100 parts by weight of the total of the other high component.
Specifically, 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), solution polymerization styrene-butadiene copolymer (SSBR), 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), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc., Any one or mixtures of two or more of these may be used.
In addition, the rubber composition according to another embodiment of the present invention may include 0.1 to 200 parts by weight of inorganic filler based on 100 parts by weight of the modified conjugated diene-based polymer.
In addition, the rubber composition according to another embodiment of the present invention may include 10 parts by weight to 150 parts by weight, specifically 50 parts by weight to 100 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer. The filler may be a silica-based filler, a carbon black-based filler, or a combination thereof.
On the other hand, when the silica-based filler is used as the filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by combining the silica particles of the filler with the modified conjugated diene-based polymer terminal. In addition, the rubber composition according to an embodiment of the present invention may be used with a silane coupling agent to improve the reinforcement and low heat generation when using a silica-based filler as a filler.
Specific examples of the silane coupling agent 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-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.
In the rubber composition according to one embodiment of the present invention, a modified conjugated diene-based polymer having a functional group having high affinity with a silica-based filler as an active moiety is used as the rubber component. The compounding amount can be reduced than usual. Specifically, 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 silica-based filler. When used in the above range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, 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.
In addition, 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.
In addition, the rubber composition according to an embodiment of the present invention, in addition to the components described above, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.
In addition, 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 based on 100 parts by weight of the rubber component, for example, 10 parts by weight to 100 parts by weight, specifically 20 parts by weight to 80 parts by weight, based on 100 parts by weight of the conjugated diene polymer. May be included. If, when the process oil is included in the content, it is possible to prevent the degradation of the tensile strength, low heat generation (low fuel efficiency) of the vulcanized rubber.
In addition, as 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.
Accordingly, 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.
In addition, the present invention provides a tire manufactured using the rubber composition.
The tire may include a tire or a tire tread.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.
Example 1
Into a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3 butadiene, 5000 g of normal hexane, 0.86 g of DTP (2,2-di (2-tetrahydrofuryl) propane) was added as a polar additive and the temperature inside the reactor was adjusted. It heated up at 40 degreeC. When the internal temperature of the reactor reached 40 ° C, 4 mmol of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. After 20 minutes, 20 g of 1,3-butadiene was added to cap the SSBR ends with butadiene. 3- (dimethyl (3- (oxirane-2-yl-methoxy) propyl) silyl) -N- (3- (dimethyl (3- (oxirane-2-yl-methoxy) silyl) propyl after 5 minutes ) -N- (3-triethoxysilyl) propyl) propan-1-amine (3-dimethyl (3- (oxira-2-yl-methoxy) propyl) silyl) -N- (3- (dimethyl (3- 4 mmol of (oxiran-2-yl-methoxy) silyl) propyl) -N- (3-triethoxysilyl) propyl) propan-1-amine) was added and denatured for 15 minutes. Then, the polymerization was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved 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 styrene-butadiene copolymer.
Example 2
3- (dimethyl (3- (oxirane-2-yl-methoxy) propyl) silyl) -N- (3- (dimethyl (3- (oxirane-2-yl-methoxy) silyl) propyl) -N 3-((3-ethoxypropyl) dimethylsilyl) -N- (3-((3-ethoxypropyl) dimethylsilyl) propyl) instead of-(3-triethoxysilyl) propyl) propan-1-amine -N- (3- (triethoxysilyl) propyl) propan-1-amine (3-((3-ethoxypropyl) dimethylsilyl) -N- (3-((3-ethoxypropyl) dimethylsilyl) propyl) -N- ( A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the modification reaction was performed using 3- (triethoxysilyl) propyl) propan-1-amine).
Comparative Example 1
A commercially available commercial styrene-butadiene copolymer (5025-2HM grade, LANXESS) was used for the experiment.
Comparative Example 2
3- (dimethyl (3- (oxirane-2-yl-methoxy) propyl) silyl) -N- (3- (dimethyl (3- (oxirane-2-yl-methoxy) silyl) propyl) -N The modified styrene-butadiene air was prepared in the same manner as in Example 1 except that the modification reaction was performed by using chlorodimethylsilane instead of-(3-triethoxysilyl) propyl) propan-1-amine. The coalescence was prepared.
Experimental Example 1
The weight average molecular weight (Mw), the number average molecular weight (Mn), the polydispersity index (PDI), and component analysis of the modified styrene-butadiene copolymers of Examples 1 and 2, Comparative Examples 1 and 2, respectively And pattern viscosity (MV) were measured, respectively. The results are shown in Table 1 below.
1) Component Analysis
Styrene derived units (SM) and vinyl content in each copolymer were measured using NMR.
2) Molecular Weight Analysis
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of each copolymer were measured by gel permeation chromatograph (GPC) analysis under 40 ° C. At this time, the column (column) was used in combination with two bags of PLgel Olexis of Polymer Laboratories Co., Ltd. and one PLgel mixed-C column, all of the newly replaced column was a mixed bed column. In addition, PS (polystyrene) was used as the GPC standard material in the molecular weight calculation. The polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by the above method.
3) Mooney viscosity analysis
The Mooney viscosity of each copolymer was measured by MV-2000 (Alpha Technologies Co., Ltd.) for 15 minutes or more of each sample weight 15g or more for 1 minute and then at 100 ℃ for 4 minutes.
Experimental Example 2
Tensile and viscoelastic properties were measured to compare and analyze the physical properties of the rubber composition and the molded article prepared from the copolymers of Examples 1 and 2 and Comparative Examples 1 and 2, respectively. The results are shown in Table 2 below.
1) Preparation of Rubber Composition
Each rubber composition was prepared through a first stage kneading process and a second stage kneading process. At this time, the amount of the substance except the modified conjugated diene copolymer is shown based on 100 parts by weight of the modified conjugated diene copolymer. In the first stage kneading, 137.5 parts by weight of each modified conjugated diene copolymer, 70 parts by weight of silica, bis (3-triethoxysilylpropyl) tetrasulfate as a silane coupling agent using a half-variety mixer equipped with a temperature controller. 11.2 parts by weight of feed, 25 parts by weight of process oil (TDAE), 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid and 1 part by weight of wax Kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at the discharge temperature of 145 ° C to 155 ° C. In the second stage kneading, after cooling the primary blend to room temperature, 1.75 parts by weight of a rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2 parts by weight of vulcanization accelerator are added to the kneader, followed by mixing at a temperature of 100 ° C. or lower, and then A blend was obtained. Each rubber composition was then prepared by a curing process for 100 to 20 minutes.
2) tensile properties
Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester to obtain tensile strength and tensile stress at 300% elongation.
3) viscoelastic properties
The viscoelastic properties were measured by using a dynamic mechanical analyzer (TA, Inc.) in which the deformation was changed at a frequency of 10 Hz and each measurement temperature (-60 ° C. to 60 ° C.) in a torsion mode. The higher the low temperature 0 ° C Tan δ, the better the wet road surface resistance. The lower the high temperature 60 ° C Tan δ, the lower the hysteresis loss, and the lower the cloud resistance (fuel efficiency).
As shown in Table 2, the tensile properties and viscoelastic properties of the rubber composition comprising the modified styrene-butadiene copolymer of Example 1 and Example 2 prepared using a modifier according to an embodiment of the present invention And it was confirmed that compared to the rubber composition comprising a copolymer of Comparative Example 2.
Specifically, the styrene-butadiene copolymer of Comparative Example 1 in which the rubber composition comprising the modified styrene-butadiene copolymers of Examples 1 and 2 prepared by using the modifier according to an embodiment of the present invention is not modified Tan δ at 0 ° C. was increased (Index value improved) and Tan at 60 ° C. compared with the rubber composition comprising the modified styrene-butadiene copolymer of Comparative Example 2 modified with a rubber composition and a conventional modifier It was confirmed that the value of δ decreased (Index value improved). This is a result showing that the modified styrene-butadiene copolymer prepared by using the modifier according to the embodiment of the present invention has excellent resistance and running resistance characteristics on the road surface, and high fuel efficiency.
Claims (25)
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 6 carbon atoms,
R 2 , R 3 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms,
R 1 and R 4 are each independently of the other -COR 7 or -COR 7 R 8 ,
Wherein C is a C 1-6 alkylene.
In Chemical Formula 1,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 6 carbon atoms,
R 9 , R 10 and R 11 are independently of each other a C 1 to C 3 alkoxy group.
Formula 1 is a modifier represented by the following formula (2) or (3):
[Formula 2]
[Formula 3]
The modifier is a modifier for a conjugated diene polymer.
The conjugated diene polymer is a modifier of a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 6 carbon atoms,
R 2 , R 3 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms,
R 1 and R 4 are each independently of the other -COR 7 or -COR 7 R 8 ,
In the above C is a modified conjugated diene-based polymer that is alkylene having 1 to 6 carbon atoms.
In Chemical Formula 1,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 6 carbon atoms,
R 9 , R 10 and R 11 are independently a conjugated diene-based polymer that is an alkoxy group having 1 to 3 carbon atoms.
Wherein said polymer is a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 1,000 g / mol to 3,000,000 g / mol.
The polymer is a modified conjugated diene-based polymer having a polydispersity index of 0.5 to 10.
The polymer is modified conjugated diene-based polymer having a vinyl content of 5% by weight.
2) A method of preparing a modified conjugated diene-based polymer comprising the step of reacting the active polymer with a modifier represented by the formula (1):
[Formula 1]
In Chemical Formula 1,
A and B are independently of each other an alkylene group having 1 to 10 carbon atoms,
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, -COR 7 or -COR 7 R 8 ,
At least one of R 1 , R 2 and R 3 is -COR 7 or -COR 7 R 8 , at least one of R 4 , R 5 and R 6 is -COR 7 or -COR 7 R 8 ,
Q is -CSiR 9 R 10 R 11 ,
In the above, C is alkylene having 1 to 10 carbon atoms,
R 7 is alkyl having 1 to 6 carbon atoms,
R 8 is an epoxy group,
R 9 , R 10 and R 11 are each independently an alkoxy group having 1 to 6 carbon atoms.
The organoalkali metal compound is a method for producing a modified conjugated diene-based polymer that is used in 0.01 mmol to 10 mmol based on a total of 100 g of the monomer.
The organoalkali metal compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, phenyllithium, 1-naphthyl Lithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, Of the modified conjugated diene-based polymer is one or more selected from the group consisting of lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropylamide Manufacturing method.
The polymerization of step 1) is a method for producing a modified conjugated diene-based polymer further by adding a polar additive.
The polar additive is a method for producing a modified conjugated diene-based polymer is added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer.
Formula 1 is a method for producing a modified conjugated diene polymer that is a compound represented by the following formula (2) or (3):
[Formula 2]
[Formula 3]
The compound represented by Formula 1 is a method for producing a modified conjugated diene-based polymer that is used in a ratio of 0.1 mol to 10 mol relative to 1 mol of the organic alkali metal compound.
The rubber composition comprises a modified conjugated diene-based polymer in 20 to 100% by weight.
The rubber composition comprises 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the polymer.
The filler is a silica-based filler, a carbon black filler or a combination thereof.
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