KR20170106770A - Alkoxysillane modifying agent comprising tertiary amino group and preparation method of modified conjugated diene polymer using the same - Google Patents
Alkoxysillane modifying agent comprising tertiary amino group and preparation method of modified conjugated diene polymer using the same Download PDFInfo
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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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- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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Abstract
Description
The present invention relates to an alkoxysilane-based modifier comprising at least three tertiary amino groups in a molecule, a modified conjugated diene-based polymer containing the alkoxysilane-based modifier-derived functional group, a method for producing the modified conjugated diene-based polymer, To a rubber composition comprising a polymer.
In recent years, as a rubber material for a tire, a conjugated diene polymer having low rolling resistance, excellent abrasion resistance, tensile properties, and adjustment stability typified by a wet skid resistance has been required in recent years in response to demand for low fuel consumption in automobiles.
In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As the evaluation index of such vulcanized rubber, repulsive elasticity of 50 DEG C to 80 DEG C, tan delta, Goodrich heat, and the like are used. That is, a rubber material having a large rebound resilience at that temperature or a small tan δ or Goodrich heating is preferable.
Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem of low wet skid resistance. Recently, a conjugated diene (co) polymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) is prepared by emulsion polymerization or solution polymerization and is used as a rubber for a tire . Of these, the greatest advantage of solution polymerization over emulsion polymerization is that vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled and molecular weight and physical properties, etc., can be controlled by coupling, It can be adjusted. Therefore, it is easy to change the structure of the finally prepared SBR or BR rubber, and it is possible to reduce the movement of chain ends due to bonding or modification of chain ends and to increase the bonding force with a filler such as silica or carbon black, It is widely used as rubber material for tires.
When such a solution-polymerized SBR is used as a rubber material for a tire, the glass transition temperature of the rubber is increased by increasing the vinyl content in the SBR, so that the tire required properties such as running resistance and braking force can be controlled, Adjustment can reduce fuel consumption.
The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and chain ends of the formed polymer are bonded or denatured by using various modifiers.
For example, US Pat. No. 4,397,994 discloses a technique in which an active anion at the chain terminal of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, a monofunctional initiator, is bonded using a binder such as a tin compound Respectively.
On the other hand, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, low hysteresis loss property and wet skid resistance are improved. However, silica having a hydrophilic surface compared to carbon black on the hydrophobic surface has a disadvantage that the affinity with the rubber is low and the dispersibility is poor. Therefore, in order to improve the dispersibility or to provide the bond between the silica and the rubber, It is necessary to use a lingering agent.
Accordingly, a method of introducing a functional group having affinity or reactivity with silica to the end of the rubber molecule has been attempted, but the effect is insufficient.
Therefore, it is necessary to develop a rubber having high affinity with a filler including silica.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and it is an object of the present invention to provide an alkoxysilane-based modifier comprising at least three tertiary amino groups in a molecule.
Another object of the present invention is to provide a modified conjugated diene-based polymer containing a functional group derived from the alkoxysilane-based modifier and exhibiting excellent affinity for a filler in a rubber composition.
It is still another object of the present invention to provide a method for producing the modified conjugated diene-based polymer using the alkoxysilane-based modifier.
It is still another object of the present invention to provide a rubber composition comprising the modified conjugated diene polymer.
According to one embodiment of the present invention, there is provided an alkoxysilane-based modifier represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
In Formula 1,
R 1 to R 5 are each independently a monovalent hydrocarbon group of 1 to 10 carbon atoms or a functional group of the following formula (2), provided that at least one of R 1 to R 5 is a functional group of the following formula (2)
R 6 and R 7 are each independently a divalent hydrocarbon group of 1 to 10 carbon atoms, and
p is an integer of 1 to 20,
(2)
In Formula 2,
R 8 is a divalent hydrocarbon group of 1 to 10 carbon atoms,
A 1 to A 3 are each independently selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a halogen group, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms .
According to another embodiment of the present invention, there is provided a modified conjugated diene polymer comprising a functional group derived from an alkoxysilane-based modifier represented by the general formula (1).
According to another embodiment of the present invention, there is provided a process for producing an activated polymer, which comprises 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 to prepare an alkali metal- And reacting the activated polymer with an alkoxysilane compound represented by the formula (1). The present invention also provides a process for producing the modified conjugated diene polymer.
According to still another embodiment of the present invention, there is provided a rubber composition comprising the modified conjugated diene polymer.
The alkoxysilane-based modifier represented by the formula (1) according to the present invention contains at least three tertiary amino groups in the molecule, so that when used as a modifier of the conjugated diene polymer, the alkoxysilane modifier shows excellent affinity to the conjugated diene polymer chain A functional group such as a tertiary amino group can be provided.
The modified conjugated diene polymer according to the present invention contains a functional group derived from the alkoxysilane-based modifier of the formula (1), for example, a tertiary amino group, so that it can exhibit excellent affinity for a filler, have.
Further, by using the alkoxysilane-based modifier of the above formula (1), the functional group capable of exhibiting excellent affinity for a filler, such as a tertiary amino group, can be easily introduced into the conjugated diene-based polymer.
In addition, the rubber composition according to the present invention can improve the processability of the rubber composition by preventing the aggregation of the filler in the rubber composition and enhancing the dispersibility of the filler by including the modified conjugated diene polymer having excellent affinity with the filler. As a result, it is possible to improve the physical properties of a molded article produced using the rubber composition, and in particular to improve tensile strength, abrasion resistance, rolling resistance, wet road surface resistance and resistance to run resistance in a tire.
Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.
The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.
According to one embodiment of the present invention, at least three tertiary amino groups are contained in the molecule to easily introduce and modify the tertiary amino group as a filler affinity functional group to the conjugated diene polymer, There is provided a modifier comprising an alkoxysilane-based compound represented by the following formula (1) capable of improving the workability of a rubber composition by increasing the dispersibility of a filler in the rubber composition:
[Chemical Formula 1]
In Formula 1,
R 1 to R 5 are each independently a monovalent hydrocarbon group of 1 to 10 carbon atoms or a functional group of the following formula (2), provided that at least one of R 1 to R 5 is a functional group of the following formula (2)
R 6 and R 7 are each independently a divalent hydrocarbon group of 1 to 10 carbon atoms, and
p is an integer of 1 to 20,
(2)
In Formula 2,
R 8 is a divalent hydrocarbon group of 1 to 10 carbon atoms,
A 1 to A 3 are each independently selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a halogen group, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms .
In the present invention, the term " at least " represents a minimum, and may be, for example, " to more than one ". That is, at least three may represent at least three or more than three.
Specifically, in Formula 1, R 1 to R 5 each independently represent an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group; An alkenyl group having 2 to 10 carbon atoms; An alkynyl group having 2 to 10 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group; An aryl group having 6 to 10 carbon atoms such as a phenyl group; An alkylaryl group having 7 to 10 carbon atoms such as a 4-methylphenyl group; An arylalkyl group having 7 to 10 carbon atoms such as a benzyl group; And the functional group of Formula 2, provided that at least one of R 1 to R 5 is a functional group of Formula 2. More specifically, each of R 1 to R 5 may independently be an alkyl group having 1 to 10 carbon atoms or a functional group represented by the general formula (2), provided that at least one of R 1 to R 5 is a functional group represented by the general formula (2).
When any one of R 1 to R 5 is a functional group of Formula 2, R 8 in Formula 2 is specifically a straight or branched alkylene group having 2 to 8 carbon atoms, A straight chain alkylene group having 3 to 6 carbon atoms such as a propylene group, a butylene group or a hexylene group.
Specifically, in formula (2), A 1 to A 3 each independently represent an alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group or propoxy group; An alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group or propyl group; And a halogen group such as fluoro, chloro or bromo, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms. More specifically, in Formula 2, A 1 to A 3 each independently represents a halogen group or an alkoxy group having 1 to 4 carbon atoms, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 4 carbon atoms.
In the above formula (1), R 6 and R 7 are each independently a linear or branched alkylene group having 2 to 8 carbon atoms, more specifically, a straight chain or branched alkylene group having 3 to 6 carbon atoms such as a propylene group, a butylene group or a hexylene group, Alkylene group.
In the above formula (1), p may be an integer of 1 to 10, more specifically an integer of 2 to 10, more specifically an integer of 2 to 5.
More specifically, the modifier comprising the alkoxysilane-based compound represented by Formula 1 according to an embodiment of the present invention is a compound represented by Formula 1 wherein R 1 to R 4 are each independently an alkyl group having 1 to 10 carbon atoms, Wherein R 5 is a functional group represented by the general formula (2), R 6 and R 7 are each independently a linear or branched alkylene group having 2 to 8 carbon atoms, and p is an integer of 1 to 10 Wherein R 8 is a linear or branched alkylene group having 2 to 8 carbon atoms, A 1 to A 3 each independently represent an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms And a halogen group, provided that at least one of A 1 to A 3 may be an alkoxy group having 1 to 6 carbon atoms.
More specifically, the modifier comprising the alkoxysilane compound represented by Formula 1 according to an embodiment of the present invention is characterized in that, in Formula 1, R 1 to R 4 each independently represent an alkyl group having 1 to 10 carbon atoms, Or an alkyl group having 1 to 4 carbon atoms, R 5 is a functional group of the above formula (2), R 6 and R 7 are each independently a linear alkylene group having 3 to 6 carbon atoms, and p is an integer of 2 to 5 Wherein R 8 is a straight-chain alkylene group having 3 to 6 carbon atoms, and A 1 to A 3 each independently represent an alkoxy group having 1 to 4 carbon atoms.
More specifically, the alkoxysilane-based compound represented by Formula 1 according to an embodiment of the present invention may be a compound represented by Formula 3 or 4, and any one or a mixture of the two may be used as a modifier.
(3)
[Chemical Formula 4]
The alkoxysilane-based modifier represented by the formula (1) according to an embodiment of the present invention may be a modifier for modifying the structure, properties, physical properties, etc. of rubber, and particularly, a conjugated diene such as a butadiene polymer or a styrene-butadiene copolymer And may be easily used as a modifier of the polymer.
Specifically, the modifier comprising an alkoxysilane compound represented by formula (1) according to an embodiment of the present invention, when used as a modifier of a conjugated diene polymer, is bonded to the conjugated diene polymer in the form of a tertiary amino group. Since the modified conjugated diene polymer has a structure containing a large number of tertiary amino groups in the molecule, the modified conjugated diene polymer can exhibit a better affinity for a filler, especially a silica filler, in a rubber composition, The dispersibility can be enhanced. As a result, the processability of the rubber composition comprising the modified conjugated diene polymer can be improved, and the physical properties of the finally obtained molded article, particularly, the tensile strength, abrasion resistance, rolling resistance, wet road surface resistance and anti- have.
Thus, according to another embodiment of the present invention, there is provided a modified conjugated diene polymer modified by a modifier comprising the alkoxysilane compound of Formula 1.
Specifically, the modified conjugated diene polymer may include a functional group derived from the alkoxysilane compound of Formula 1, for example, a tertiary amino group. More specifically, one or more tertiary amino groups may be bonded to the conjugated diene-based polymer chain.
The conjugated diene-based polymer may be a homopolymer of a conjugated diene-based monomer, or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.
When the modified conjugated diene-based polymer is a copolymer, the copolymer is a random copolymer having a structural unit derived from a conjugated diene-based monomer and a structural unit derived from an aromatic vinyl-based monomer, Lt; / RTI >
Specifically, the modified conjugated diene polymer may have a narrow molecular weight distribution (Mw / Mn) of 1.1 to 5.0. When the molecular weight distribution of the modified conjugated diene polymer is more than 5.0 or less than 1.1, there is a possibility that the tensile property and the viscoelasticity are lowered when applied to a rubber composition. The molecular weight distribution of the modified conjugated diene polymer may be specifically from 1.3 to 3.0 in view of the tensile property of the polymer and the remarkable effect of improving the viscoelasticity according to the molecular weight distribution control.
In the present invention, the molecular weight distribution of the modified butadiene polymer can be calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Wherein the number average molecular weight (Mn) is a common average of the molecular weight of the individual polymers calculated by measuring the molecular weights of the n polymer molecules and calculating the sum of the molecular weights and dividing by n, and the linear (Mw) Lt; / RTI > All molecular weight averages can be expressed in grams per gram (g / mol).
In the present invention, the weight-average molecular weight and the number-average molecular weight are the polystyrene-reduced molecular weights analyzed by gel permeation chromatography (GPC), respectively.
The modified conjugated diene polymer may have a number average molecular weight (Mn) of 50,000 g / mol to 2,000,000 g / mol, and more preferably 200,000 g / mol to 1,000,000 g / mol. The modified conjugated diene polymer may have a weight average molecular weight (Mw) of 100,000 g / mol to 4,000,000 g / mol, and more specifically 300,000 g / mol to 1,500,000 g / mol.
When the straight chain (Mw) of the modified conjugated diene polymer is less than 100,000 g / mol / mol or the number average molecular weight (Mn) is less than 50,000 g / mol, there is a fear of deterioration of tensile properties when applied to a rubber composition. When the linear molecular weight (Mw) exceeds 4,000,000 g / mol or the number average molecular weight (Mn) exceeds 2,000,000 g / mol, the workability of the rubber composition deteriorates due to the deteriorated workability of the modified conjugated diene polymer, The kneading becomes difficult, and it may be difficult to sufficiently improve the physical properties of the rubber composition.
More specifically, when the modified conjugated diene polymer according to an embodiment of the present invention satisfies both the weight average molecular weight (Mw) and the number average molecular weight condition together with the molecular weight distribution described above, The tensile properties, the viscoelasticity and the workability can be improved and the balance can be improved.
The modified conjugated diene polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% by weight to 50% by weight. When the vinyl content is in the above range, Can be adjusted to an appropriate range. Therefore, when the tire is applied to a tire, it is excellent in physical properties required for a tire such as a running resistance and a braking force, and also has an effect of reducing fuel consumption.
Herein, the vinyl content is expressed as a percentage of the content of the 1,2-added conjugated diene monomer, not 1,4-addition relative to the total weight of the conjugated diene polymer composed of the monomer having vinyl group or the conjugated diene monomer.
In addition, the modified conjugated diene polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) at 100 ° C of 40 to 60, specifically 40 to 50. It is possible to exhibit better processability when having the Mooney viscosity in the above-mentioned range.
In the present invention, the Mooney viscosity can be measured using a Mooney viscometer, for example, Monsanto MV2000E at 100 using Rotor Speed 2 0.02 rpm, Large Rotor. At this time, the used sample is allowed to stand at room temperature (23 ± 3) for more than 30 minutes, and 27 ± 3 g can be collected, filled in the die cavity, and measured by operating a platen.
According to another embodiment of the present invention, there is provided a method for producing the modified conjugated diene-based polymer using the modifier comprising the alkoxysilane-based compound represented by the formula (1).
Specifically, the production method comprises 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 to produce an active polymer having at least one terminal thereof bound with an alkali metal One); And reacting the active polymer with the alkoxysilane-based modifier represented by Formula 1 (Step 2).
The step 1 is a step for producing an active polymer having at least one terminal thereof bound with an alkali metal and is carried out 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 can do.
The polymerization of step 1 may be carried out using a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer as monomers. That is, the polymer produced by the above production method according to an embodiment of the present invention may be a conjugated diene monomer homopolymer or a copolymer derived from a conjugated diene monomer and an aromatic vinyl monomer.
Examples of the conjugated diene monomer include, but are not limited to, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, -1,3-butadiene, and the like.
When the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the conjugated diene-based monomer has a unit derived from the conjugated diene-based monomer in the finally produced modified conjugated diene-based polymer in an amount of 60% by weight or more, In an amount of 60 wt% to 90 wt%, more specifically 60 wt% to 85 wt%.
Examples of the aromatic vinyl monomer include, but not limited to, styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- -Methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.
When the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the amount of the aromatic vinyl-based monomer-derived unit in the finally produced modified conjugated diene-based polymer is 40% by weight or less, , More preferably from 10% by weight to 40% by weight, and still more specifically from 15% by weight to 40% by weight.
The hydrocarbon solvent is not particularly limited, but may be one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
The organic alkali metal compound may be used in an amount of 0.1 to 1.0 mmol based on 100 g of the total weight of the monomers.
The organic alkali metal compound is not particularly limited and includes, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- Phenyl lithium, 1-naphthyl lithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, At least one member selected from the group consisting of lithium, sodium, potassium, sodium, potassium, sodium, sodium, potassium, sodium, sodium, potassium and alkaline earth metals. .
The polymerization of step 1 may be carried out by adding a polar additive if necessary, and the polar additive may be added in an amount of 0.001 part by weight to 1.0 part by weight based on 100 parts by weight of the total weight of the monomers. Specifically, it may be added in an amount of 0.005 part by weight to 0.5 part by weight, more specifically 0.01 part by weight to 0.3 part by weight, based on 100 parts by weight of the total amount of monomers.
The polar additive may be selected from the group consisting of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloalcohol ether, dipropyl ether, ethylenedimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.
In the production 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 random copolymer can be easily formed .
The polymerization of the step 1 may be carried out through adiabatic polymerization or by isothermal polymerization.
Herein, the adiabatic polymerization represents a polymerization method comprising the step of polymerizing an organic alkali metal compound into a self-reaction heat without any heat, after the introduction of the organic alkali metal compound, wherein the isothermal polymerization is carried out by arbitrarily introducing heat Or the heat is taken to keep the temperature of the polymerizer constant.
The polymerization may be carried out in a temperature range of -20 캜 to 200 캜, specifically, in a temperature range of 0 캜 to 150 캜, more specifically, 10 캜 to 120 캜.
Step 2 is a denaturation step in which the active polymer is reacted with the alkoxysilane-based modifier represented by the formula (1) to produce a modified conjugated diene-based polymer.
The modifier for rubber represented by Formula 1 may be as described above. The modifier for rubber represented by the above formula (1) may be used in a proportion of 0.05 mol to 3.0 mol based on 1 mol of the organic alkali metal compound.
The reaction of Step 2 may be a modification reaction for introducing a functional group into the polymer, and each of the above reactions may be carried out at a temperature range of 0 ° C to 90 ° C for 1 minute to 5 hours.
The manufacturing method according to an embodiment of the present invention may further include at least one of a solvent and unreacted monomer recovery and drying as needed after the step 2.
According to another embodiment of the present invention, there is provided a rubber composition comprising the modified conjugated diene polymer.
The rubber composition may contain 0.1 to 100% by weight, specifically 10 to 100% by weight, more specifically 20 to 90% by weight, of the modified conjugated diene polymer. If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the abrasion resistance and crack resistance of a molded article produced using the rubber composition, such as a tire, may be insignificant.
In addition, the rubber composition may further include other rubber components, if necessary, in addition to the modified conjugated diene polymer, wherein the rubber component may be contained in an amount of 90 wt% or less based on the total weight of the rubber composition. Specifically, it may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.
The rubber component may be natural rubber or synthetic rubber, for example natural rubber (NR) comprising cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, poly Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber and the like may be used, and any one or a mixture of two or more thereof may be used have.
In addition, the rubber composition may contain 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.
The filler may be specifically a silica filler or a carbon black filler, and either one or a mixture of the two may be used.
More specifically, the filler may be silica, and more specifically may be wet silica (hydrosilicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and the like. More specifically, the filler may be a wet silica having the most remarkable effect of improving the fracture characteristics and the wet grip.
On the other hand, when a silica-based filler is used as the filler, a silane coupling agent may be used together to improve the reinforcing property and the low heat build-up.
Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate Monosulfide, monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl- N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. Any one or a mixture of two or more of them may be used. More specifically, in consideration of the reinforcing effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazine tetrasulfide.
Further, in the rubber composition according to the embodiment of the present invention, since the modified conjugated diene polymer in which a functional group having a high affinity for the silica-based filler is introduced into the active site as a rubber component is used, The compounding amount can be reduced more than usual. Specifically, the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight based on 100 parts by weight of the silica-based filler. When used in the above-mentioned range, gelation of the rubber component can be prevented while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 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 may further include a vulcanizing agent.
The vulcanizing agent may be specifically a sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.
In addition, the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, such as a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.
The vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
The process oil may be a paraffinic, naphthenic, or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.
Specific examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.
The rubber composition according to one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.
Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, Can be useful for the production of various industrial rubber products.
According to another embodiment of the present invention, there is provided a molded article and a tire produced using the rubber composition.
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 for illustrating the present invention, and the scope of the present invention is not limited thereto.
Example 1
270 g of styrene, 710 g of 1,3-butadiene and 5000 g of n-hexane were placed in a 20 L autoclave reactor, and 1.3 g of 2,2-bis (2-oxoranyl) propane was added as a polar additive. Lt; / RTI > When the internal temperature of the reactor reached 40 캜, 4 mmol of n-butyllithium was charged into the reactor to proceed the adiabatic temperature-rise reaction. After 20 minutes of reaction, 20 g of 1,3-butadiene was added to cap the end of the SSBR with butadiene. After 5 minutes, 4 mmol of the modifier of the following formula (3) was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added. The resultant polymer was put into hot water heated with steam and stirred to remove the solvent. The solvent was then removed by roll drying to remove the remaining solvent and water to prepare a modified styrene-butadiene copolymer.
Example 2
Modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that 4 mmol of a modifier of the following formula (4) was added in place of the modifier of the formula (3) to conduct a denaturing reaction.
Comparative Example 1
Modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that 4 mmol of tetraethoxysilane (TEOS) was added in place of the modifier of Formula 3 to conduct a denaturing reaction.
Experimental Example 1
(Mw), a number average molecular weight (Mn), a polydispersion index (PDI), a component analysis and a pattern viscosity (MV) of each of the modified styrene-butadiene copolymers of Examples 1 and 2 and Comparative Example 1, Respectively. The results are shown in Table 1 below.
1) Component analysis
The styrene derived unit (SM) and vinyl content in each copolymer were measured by NMR.
2) Molecular weight analysis
The weight average molecular weight (Mw) and number average molecular weight (Mn) of each copolymer were measured by GPC (Gel Permeation Chromatograph) analysis under the condition of 40 캜. In this case, two columns of PLgel Olexis manufactured by Polymer Laboratories and a PLgel mixed-C column were used in combination, 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. The polydispersity index (PDI) was calculated as the ratio (Mw / Mn) of the weight average molecular weight to 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) at a temperature of 100 ° C for 4 minutes after preheating two samples each weighing 15 g or more for 1 minute.
(Mmol < / RTI > based on 100 g total weight of monomer)
(Mmol < / RTI > based on 100 g total weight of monomer)
(% By weight based on total polymer weight)
(% By weight based on total polymer weight)
Experimental Example 2
Tensile properties and viscoelastic properties of the rubber compositions containing the modified styrene-butadiene copolymers of Examples 1 and 2 and Comparative Example 1 and the molded articles prepared therefrom were compared and analyzed.
1) Preparation of rubber composition
Each rubber composition was manufactured through a first stage kneading, a second stage kneading and a third stage kneading. In this case, the amount of the material except for the modified styrene-butadiene copolymer is shown based on 100 parts by weight of the modified styrene-butadiene copolymer. In the first stage kneading, 100 parts by weight of each of the above copolymers, 70 parts by weight of silica was mixed with 80 parts by weight of bis (3-triethoxysilylpropyl) tetrasulfide as a silane coupling agent using a Banbury mixer equipped with a temperature controller, 2.0 parts by weight of antioxidant, 3.0 parts by weight of zinc oxide (ZnO), 2.0 parts by weight of stearic acid, And 1.0 part by weight of wax were blended and kneaded. At this time, the temperature of the kneader was controlled and a primary blend was obtained at an outlet temperature of 140 ° C to 150 ° C. In the second stage kneading, after cooling the above-mentioned primary blend to room temperature, 1.75 parts by weight of a rubber accelerator (CZ), 1.5 parts by weight of sulfur powder and 2.0 parts by weight of a vulcanization accelerator were added to a kneader and mixed at a temperature of 60 DEG C or lower, ≪ / RTI > Thereafter, the second blend was molded in the third stage kneading and vulcanized at 180 for t90 + 10 minutes in a vulcanized press to prepare each vulcanized rubber.
2) Tensile properties
Each test piece (thickness 25 mm, length 80 mm) was manufactured in accordance with the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece and the tensile stress at 300% elongation (300% modulus) were measured. Specifically, tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester to obtain tensile strength and tensile stress values at 300% elongation.
3) Viscoelastic properties
The viscoelastic properties were measured by using a dynamic mechanical analyzer (TA) at a frequency of 10 Hz in a twist mode at various measuring temperatures (0 ° C to 60 ° C). The payne effect (ΔG ') is expressed as the difference between the minimum value and the maximum value at 0.28% to 40% of the variation, and the smaller the peening effect, the better the dispersibility of the filler. Also, the lower the tan 隆 at a high temperature of 60 캜, the lower the hysteresis loss and the lower the rolling resistance (fuel economy).
As a result of the test, the rubber composition comprising the modified styrene-butadiene polymer of Example 1 or 2 modified by using the modifier according to the present invention was superior in both tensile strength, viscoelasticity and workability as compared with Comparative Example 1.
Claims (18)
[Chemical Formula 1]
In Formula 1,
R 1 to R 5 are each independently a monovalent hydrocarbon group of 1 to 10 carbon atoms or a functional group of the following formula (2), provided that at least one of R 1 to R 5 is a functional group of the following formula (2)
R 6 and R 7 are each independently a divalent hydrocarbon group of 1 to 10 carbon atoms, and
p is an integer of 1 to 20,
(2)
In Formula 2,
R 8 is a divalent hydrocarbon group of 1 to 10 carbon atoms,
A 1 to A 3 are each independently selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a halogen group, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms .
Wherein R 1 to R 5 are each independently an alkyl group having 1 to 10 carbon atoms or a functional group represented by the following general formula (2), provided that at least one of R 1 to R 5 is a functional group represented by the general formula (2)
R 6 , R 7 and R 8 are each independently a straight or branched alkylene group having 2 to 8 carbon atoms,
A 1 to A 3 are each independently selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a halogen group, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms And
and p is an integer of 1 to 10.
Each of R 1 to R 4 is independently an alkyl group having 1 to 4 carbon atoms,
Wherein R < 5 > is a functional group of the above formula (2)
Each of R 6 to R 8 is independently a straight chain alkylene group having 3 to 6 carbon atoms,
A 1 to A 3 each independently represent an alkoxy group having 1 to 4 carbon atoms, and
And p is an integer of 2 to 5.
Wherein the alkoxysilane-based modifier comprises at least one of the following chemical formulas (3) and (4):
(3)
[Chemical Formula 4]
Wherein the modifier is a conjugated diene polymer modifying modifier.
Wherein the conjugated diene-based polymer is a conjugated diene-based monomer homopolymer or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.
[Chemical Formula 1]
In Formula 1,
R 1 to R 5 are each independently a monovalent hydrocarbon group of 1 to 10 carbon atoms or a functional group of the following formula (2), provided that at least one of R 1 to R 5 is a functional group of the following formula (2)
R 6 and R 7 are each independently a divalent hydrocarbon group of 1 to 10 carbon atoms, and
p is an integer of 1 to 20,
(2)
In Formula 2,
R 8 is a divalent hydrocarbon group of 1 to 10 carbon atoms,
A 1 to A 3 are each independently selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a halogen group, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms .
Wherein the number average molecular weight is from 50,000 g / mol to 2,000,000 g / mol, and the weight average molecular weight is from 100,000 g / mol to 4,000,000 g / mol.
And a molecular weight distribution of 1.1 to 5.0.
Wherein the modified conjugated diene polymer has a Mooney viscosity at 100 占 폚 of 40 to 60. The modified conjugated diene-
Reacting the active polymer with an alkoxysilane-based modifier represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
In Formula 1,
R 1 to R 5 are each independently a monovalent hydrocarbon group of 1 to 10 carbon atoms or a functional group of the following formula (2), provided that at least one of R 1 to R 5 is a functional group of the following formula (2)
R 6 and R 7 are each independently a divalent hydrocarbon group of 1 to 10 carbon atoms, and
p is an integer of 1 to 20,
(2)
In Formula 2,
R 8 is a divalent hydrocarbon group of 1 to 10 carbon atoms,
A 1 to A 3 are each independently selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a halogen group, provided that at least one of A 1 to A 3 is an alkoxy group having 1 to 6 carbon atoms .
Wherein the organic alkali metal compound is used in an amount of 0.1 mmol to 1.0 mmol based on 100 g of the total amount of the monomers.
Wherein the polar additive is further added during the polymerization.
Wherein the polar additive is added in an amount of 0.001 part by weight to 1.0 part by weight based on 100 parts by weight of the total amount of monomers.
Wherein the alkoxysilane-based modifier represented by the formula (1) is used in a proportion of 0.05 mol to 3.0 mol based on 1 mol of the organic alkali metal compound.
Wherein the rubber composition further comprises 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.
Wherein the filler is a silica-based filler.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210052318A (en) * | 2019-10-31 | 2021-05-10 | 주식회사 엘지화학 | Modifying agent, modified conjugated diene polymer and method for preparing thereof |
| KR20210051967A (en) * | 2019-10-31 | 2021-05-10 | 주식회사 엘지화학 | Novel compound, preparing method thereof, modified conjugated diene polymer comprising fuctional group derived vy the same and preparing method for the polymer |
| KR20210062382A (en) * | 2019-11-21 | 2021-05-31 | 주식회사 엘지화학 | Method for preparing modified conjugated diene polymer |
| CN114008087A (en) * | 2019-11-29 | 2022-02-01 | 株式会社Lg化学 | Modifier and modified conjugated diene polymer prepared using the same |
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| KR20210051967A (en) * | 2019-10-31 | 2021-05-10 | 주식회사 엘지화학 | Novel compound, preparing method thereof, modified conjugated diene polymer comprising fuctional group derived vy the same and preparing method for the polymer |
| KR20210062382A (en) * | 2019-11-21 | 2021-05-31 | 주식회사 엘지화학 | Method for preparing modified conjugated diene polymer |
| CN114008087A (en) * | 2019-11-29 | 2022-02-01 | 株式会社Lg化学 | Modifier and modified conjugated diene polymer prepared using the same |
| CN114008087B (en) * | 2019-11-29 | 2023-12-01 | 株式会社Lg化学 | Modifier and modified conjugated diene polymer prepared using the same |
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