KR102117620B1 - Modified conjugated diene polymer and method for preparing the same - Google Patents

Abstract

상기 화학식 1에서, 각 치환기의 정의는 발명의 설명 상 정의된 바와 같다.The present invention relates to a modified conjugated diene-based polymer, and more specifically, includes a conjugated diene-based monomer-derived repeating unit, and a modified conjugated diene-based functional group containing a modifier-derived functional group containing a compound represented by the following Chemical Formula 1 at one end. Provided are polymers and methods for their preparation.
[Formula 1]

In Formula 1, the definition of each substituent is as defined in the description of the invention.

Description

Modified conjugated diene-based polymer and manufacturing method therefor {MODIFIED CONJUGATED DIENE POLYMER AND METHOD FOR PREPARING THE SAME}

The present invention relates to a modified conjugated diene-based polymer, and more specifically, by including a functional group derived from a modifier excellent in affinity with the inorganic filler, a modified conjugated diene system having excellent processability, excellent tensile strength, abrasion resistance, and wet road resistance It relates to a polymer.

Recently, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer having a low rolling resistance as a tire rubber material, excellent abrasion resistance and tensile properties, and also having adjustment stability represented by wet road resistance is required.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and as the evaluation index of the vulcanized rubber, repulsive elasticity of 50 ° C to 80 ° C, tan δ, and good-rich heat are used. That is, a rubber material having high rebound resilience at the above temperature, or low tan δ, good-rich heat generation is preferable.

As the rubber material having low hysteresis loss, natural rubber, polyisoprene rubber or polybutadiene rubber, etc. are known, but they have a problem of low wet surface resistance. Accordingly, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are prepared by emulsion polymerization or solution polymerization and used as rubber for tires. . Among these, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content that regulate rubber properties can be arbitrarily controlled, and the molecular weight and physical properties, etc., can be adjusted by coupling or modification. It is adjustable. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by binding or denaturation at the chain ends, and increase the bonding strength with fillers such as silica or carbon black. It is often used as a rubber material.

When the solution-cured SBR is used as a rubber material for tires, the glass transition temperature of the rubber is increased by increasing the vinyl content in the SBR, so that the required properties of tires such as driving resistance and braking force can be adjusted, as well as the glass transition temperature. Proper adjustment can reduce fuel consumption. The solution polymerization SBR is prepared by using an anionic polymerization initiator, and the chain ends of the formed polymers are combined or modified using various denaturing agents. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using a monofunctional initiator, alkyllithium, using a binder such as a tin compound Did.

On the other hand, carbon black and silica are used as reinforcing fillers for tire treads, and when silica is used as reinforcing fillers, there is an advantage of low hysteresis loss and improved wet road resistance. However, the silica on the hydrophilic surface compared to the carbon black on the hydrophobic surface has a drawback that it has low affinity with rubber and has poor dispersibility, so that a separate silane couple is used to improve dispersibility or to impart bonds between silica and rubber. It is necessary to use a ring agent. Accordingly, a method of introducing a functional group having affinity or reactivity with silica at the end of the rubber molecule has been made, but the effect is not sufficient.

US 4397994 A

The present invention has been devised to solve the problems of the prior art, and includes a functional group derived from a modifier having excellent affinity with an inorganic filler, so that it has excellent processability despite having a high molecular weight, tensile strength, abrasion resistance and wet road resistance. It is an object to provide an excellent modified conjugated diene-based polymer and a method for manufacturing the same.

According to an embodiment of the present invention for solving the above problems, the present invention includes a conjugated diene-based monomer-derived repeating unit, and a modified group containing a functional group derived from a modifier comprising a compound represented by the following Chemical Formula 1 at one end. Provided are conjugated diene-based polymers:

[Formula 1]

In Chemical Formula 1, R ¹ is a pyrroline substituted or unsubstituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, a pyrrole substituted or unsubstituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or carbon number. It may be a piperazine substituted or unsubstituted with a monovalent hydrocarbon group of 1 to 10, R ² and R ³ may each independently be a divalent hydrocarbon group having 1 to 30 carbon atoms, R ⁴ , R ⁵ and R ⁶ may be each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, m may be an integer of 1 or 2, and n may be an integer selected from 1 to 3.

In addition, the present invention comprises the steps of polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organic metal compound to prepare an active polymer in which an organic metal is bound (S1); And it provides a modified conjugated diene-based polymer production method comprising the step of reacting (S2) with a modifier containing the active polymer and a compound represented by the following formula (1):

[Formula 1]

In Formula 1, the definition for each substituent is as defined above.

In addition, the present invention provides a modifier comprising the compound represented by Formula 1 and a method for manufacturing the same.

When a conjugated diene-based polymer is modified from a modifier excellent in affinity with the inorganic filler according to the present invention, by including a functional group derived from the modifier at one end of the polymer, the modified conjugated diene-based polymer excellent in affinity with the inorganic filler It is possible to manufacture, and the modified conjugated diene-based polymer prepared in this way has high molecular weight, has excellent processability, and has excellent effects in tensile strength, abrasion resistance, and wet road resistance.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

Terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms in order to explain his or her invention in the best way. Based on the principle of being able to be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The modified conjugated diene-based polymer according to the present invention may include a repeating unit derived from a conjugated diene-based monomer, and may include a functional group derived from a modifier comprising a compound represented by the following Chemical Formula 1 at one end:

[Formula 1]

In Formula 1, R ¹ is a pyrrolidine substituted or unsubstituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, a pyrrole substituted or unsubstituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or carbon number. It may be a piperazine substituted or unsubstituted with a monovalent hydrocarbon group of 1 to 10, R ² and R ³ may each independently be a divalent hydrocarbon group having 1 to 30 carbon atoms, R ⁴ , R ⁵ and R ⁶ may be each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, m may be an integer of 1 or 2, and n may be an integer selected from 1 to 3.

In the present invention, the term 'monovalent hydrocarbon group' refers to a monovalent atomic group in which carbon and hydrogen, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group including one or more unsaturated bonds, and an aryl group are bonded. The minimum number of carbon atoms of the substituent represented by a monovalent hydrocarbon may be determined according to the type of each substituent.

In the present invention, the term 'divalent hydrocarbon group' refers to a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including at least one unsaturated bond, and an arylene group, such as carbon and hydrogen bonded 2 It may mean a valence atom group, and the minimum number of carbon atoms of a substituent represented by a divalent hydrocarbon may be determined according to the type of each substituent.

In a specific example, in Formula 1, R ¹ is a pyrrolidine substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, a pyrrole substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, or carbon number 1 unsubstituted or substituted with 1 to 5 alkyl groups of piperazine (piperazine) provided that, pyrrolidine, pyrrole, or may be combined with the N atom R ² of piperazine, R ² and R ³ having 1 to 20 carbon atoms each independently It may be an alkylene group, R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, m is 1 or 2 It may be an integer of, n may be an integer selected from 1 to 3.

As a more specific example, in Formula 1, R ¹ is a pyrrolidine substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, a pyrrole substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, or carbon number. 1 to a group of 5 can be coupled with substituted or unsubstituted piperazine (piperazine) provided that, pyrrolidine, pyrrole, or N atoms R ² of piperazine, R ² and R ³ are C 1 -C each independently 10 may be an alkylene group, R ⁴ , R ⁵ and R ⁶ may each independently be an alkyl group having 1 to 10 carbon atoms, m may be an integer of 1 or 2, and n may be an integer selected from 1 to 3. .

In the present invention, the term 'alkyl group (alkyl group)' may mean a monovalent aliphatic saturated hydrocarbon, linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, secbutyl (sec-butyl), ter It may be meant to include both branched alkyl groups such as tert-butyl and neo-pentyl.

In the present invention, the term 'alkylene group (alkylene group)' may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

In the present invention, the term 'cycloalkyl group (cycloalkyl group)' may refer to a cyclic saturated hydrocarbon, or to include all of cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.

The term 'aryl group' in the present invention may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are combined. hydrocarbon).

According to an embodiment of the present invention, the compound represented by Formula 1 may be one or more selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In the above formulas 1-1 to 1-5, Et is an ethyl group.

As described above, according to the present invention, when a conjugated diene-based polymer is denatured from a modifier excellent in affinity with an inorganic filler, including the compound represented by Formula 1, by including a functional group derived from the modifier at one end of the polymer , It is possible to manufacture a modified conjugated diene-based polymer having excellent affinity with an inorganic filler, and the modified conjugated diene-based polymer thus prepared has excellent processability even with a high molecular weight, and has excellent effects in tensile strength, abrasion resistance, and wet road resistance. .

The repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed by polymerization of the conjugated diene-based monomer, and the conjugated diene-based monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene. , Piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom). It may be one or more selected.

Meanwhile, the modified conjugated diene-based copolymer may be, for example, a copolymer further comprising an aromatic vinyl monomer-derived repeating unit together with the repeating unit derived from the conjugated diene-based monomer.

The repeating unit derived from the aromatic vinyl monomer may mean a repeating unit formed when the aromatic vinyl monomer is polymerized, and the aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 4-propyl. It may be one or more selected from the group consisting of styrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.

When the modified conjugated diene-based polymer is a copolymer containing a repeating unit derived from an aromatic vinyl monomer, the modified conjugated diene-based polymer is 50 to 95% by weight, 55 to 90% by weight, or 60 to 60% of the repeating unit derived from the conjugated diene-based monomer. At 90% by weight, the aromatic vinyl monomer-derived repeating unit may contain 5 to 50% by weight, 10 to 45% by weight, or 10 to 40% by weight, and within this range, excellent rolling resistance, wet road resistance and wear resistance It works.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, the balance between the properties is excellent. The random copolymer may mean that the repeating units constituting the copolymer are arranged in disorder.

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,00,000 g / mol, 50,000 g / mol to 800,000 g / mol, or 100,000 g / mol to 500,000 g / mol, and a weight average molecular weight (Mw) of 10,000 g / mol to 5,000,000 g / mol, 10,000 g / mol to 3,000,000 g / mol, 50,000 g / mol to It may be 1,500,000 g / mol, or 100,000 g / mol to 1,000,000 g / mol, and within this range, there is an excellent effect of rolling resistance and wet road resistance. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1 to 5, 1 to 4, or 1 to 3, and within this range, the physical property balance between properties has an excellent effect.

As another example, the modified conjugated diene-based polymer may have a Mooney viscosity of 100 ° C. or more, 40 or more, 40 to 110, or 40 to 100, and has excellent processability and productivity within this range.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, 10 wt% to 50 wt%, or 20 wt% to 50 wt%, and the glass transition temperature within this range. Since it can be adjusted to an appropriate range, it has excellent effects of rolling resistance, wet road resistance and low fuel efficiency. Here, the vinyl content refers to the content of 1,2-added conjugated diene-based monomers rather than 1,4-added to 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl-based monomer. You can.

Meanwhile, in the present invention, the terms 'derived repeating unit' and 'derived functional group' may refer to a component, a structure originating from a substance, or the substance itself.

The method for producing a modified conjugated diene-based polymer according to the present invention is to prepare an active polymer in which an organic metal is bound by polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organic metal compound. Step S1; And it may include a step (S2) of reacting with a modifier containing the active polymer and a compound represented by the following formula (1).

[Formula 1]

Definitions for each substituent in Formula 1 are as defined above.

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.

According to an embodiment of the present invention, the compound represented by Chemical Formula 1 may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of monomers.

According to an embodiment of the present invention, the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol based on 100 g of monomers.

The organometallic compound is, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naph Tilithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , Lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

On the other hand, the polymerization of the step (S1) may be carried out by including a polar additive, the polar additive can be added from 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g based on 100g total monomer have. In addition, the polar additives are tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane , Bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine. It may be an amine or tetramethylethylenediamine, and may be the same or different from a polar additive that may be added in the preparation of the amino silane-based compound, and when the polar additive is included, a conjugated diene-based monomer, or a conjugated diene-based monomer and In the case of copolymerizing aromatic vinyl-based monomers, there is an effect of inducing that a random copolymer can be easily formed by compensating for the difference in their reaction rates.

The polymerization of the step (S1) may be, for example, anionic polymerization, and specifically, a living anionic polymerization having an anion active site at the polymerization end by a growth polymerization reaction by anions. In addition, the polymerization of the step (S1) may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (single polymerization), and the constant temperature polymerization includes the step of polymerizing with the reaction heat itself without adding any heat after the introduction of the organometallic compound. It may mean a polymerization method, and the elevated temperature polymerization may mean a polymerization method in which the temperature is increased by optionally adding heat after the organometallic compound is introduced, and the isothermal polymerization is performed after the organometallic compound is introduced. It may mean a polymerization method in which heat is increased or heat is taken to maintain a constant temperature of the polymer. In addition, the polymerization of the step (S1) is, for example, the polymerization may be carried out in a temperature range of -20 ℃ to 200 ℃, 0 ℃ to 150 ℃, or 10 ℃ to 120 ℃.

The active polymer prepared by the step (S1) may mean a polymer in which a polymer anion and an organometallic cation are combined.

According to an embodiment of the present invention, the molar ratio of the modifier including the compound represented by Chemical Formula 1 and the organometallic compound may be 1: 0.1 to 1:10, and a denaturation reaction of optimal performance may be performed within this range. It is possible to obtain a conjugated diene polymer having a high modification rate.

The reaction of the step (S2) is a denaturation reaction for introducing a functional group derived from the denaturant into the active polymer, and may be performed for 1 minute to 5 hours at 0 ° C to 90 ° C.

In addition, according to an embodiment of the present invention, the method for preparing the modified conjugated diene polymer may be performed by a batch type (batch type) or a continuous polymerization method including one or more reactors.

The modified conjugated diene-based polymer manufacturing method may further include at least one of the solvent and unreacted monomer recovery and drying steps, if necessary, following the (S2) step of the present invention.

The denaturant according to the present invention may include a compound represented by Formula 1 below:

[Formula 1]

In Formula 1, the definition for each substituent is as defined above.

The modifier of the present invention has an excellent affinity with inorganic fillers, particularly silica-based fillers, and thus has an effect of increasing the dispersing power between the polymer and filler modified from the modifier.

According to the present invention, a rubber composition comprising the modified conjugated diene-based polymer is provided.

The rubber composition may include the modified conjugated diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight, and within this range, tensile strength, abrasion resistance, etc. Has excellent mechanical properties, and has an excellent balance between properties.

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 component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be contained in 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples 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, which have been modified or purified from the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene) -Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, synthetic rubber such as halogenated butyl rubber, etc., any one or a mixture of two or more of them can be used. have.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, and may be, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica, preferably improving the breaking effect and wettability. It may be wet silica having the best compatibility of wet grip. In addition, the rubber composition may further include a carbon black-based filler, if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing property and low heat generation property may be used together, and as a specific example, the silane coupling agent is bis (3-triethoxysilylpropyl) tetrasulfide , Bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilyl Propyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulf Feed, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethyl Silane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, or the like, and any one or a mixture of two or more thereof may be used. Preferably, when considering the effect of improving the reinforcing properties, it may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer having a functional group having high affinity with silica introduced at an active site is used as a rubber component, the compounding amount of the silane coupling agent is usually It may be reduced than the case, and accordingly, the silane coupling agent may be used in 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of silica, and the effect as a coupling agent within this range While sufficiently exhibited, there is an effect of preventing the gelation of the rubber component.

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 specifically be 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, and at the same time securing the required elastic modulus and strength of the vulcanized rubber composition and low fuel efficiency. It has an excellent effect.

The rubber composition according to an embodiment of the present invention, in addition to the above-mentioned components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, scorch inhibitors, zinc white, Stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG Guanidine-based compounds such as (diphenylguanidine) may be used, and 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 acts as a softening agent in the rubber composition, and may be, for example, a paraffin-based, naphthenic-based, or aromatic-based compound, and when considering tensile strength and abrasion resistance, considering the aromatic process oil, hysteresis loss and low temperature properties Naphthenic or paraffinic process oils can be used. The process oil may be included, for example, in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, there is an effect of preventing deterioration of tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

The anti-aging agent is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, and may be used in an amount of 0.1 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 kneader such as a Banbury mixer, a roll, an internal mixer, etc., by the above-described formulation, and is low heat-resistant and wear-resistant by a vulcanization process after molding. This excellent rubber composition can be obtained.

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreatic, or bead coated rubber, each member of a tire, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture 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 by examples. However, the following examples are only intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

In a 20L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene and 5,000 g of normal hexane, and 0.86 g of ditetrahydrofurylpropane (2,2-bis (2-oxolanyl) propane) are added as polar additives, and then inside the reactor. The temperature was raised to 50 ° C. When the temperature inside the reactor reached 50 ° C, 4 mmol of n-butyllithium was introduced into the reactor to perform an adiabatic temperature increase reaction. After the adiabatic heating reaction was over, 20 g of 1,3-butadiene was added to cap the end of the polymer with butadiene. After 20 minutes, 4.3 mmol of the compound represented by the following Chemical Formula 1-1 was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added. The resultant polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll dried to remove the residual amount of solvent and water to prepare a modified conjugated diene-based polymer. The results of the analysis of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.

[Formula 1-1]

Example 2

In Example 1, it was carried out in the same manner as in Example 1, except that 4.3 mmol of the compound represented by the following Chemical Formula 1-2 was added instead of the compound represented by Chemical Formula 1-1.

[Formula 1-2]

Example 3

In Example 1, it was carried out in the same manner as in Example 1, except that 4.3 mmol of the compound represented by Chemical Formula 1-3 was added instead of the compound represented by Chemical Formula 1-1.

[Formula 1-3]

Example 4

In Example 1, it was carried out in the same manner as in Example 1, except that 4.3 mmol of the compound represented by the following Formula 1-4 was added instead of the compound represented by the Formula 1-1.

[Formula 1-4]

Example 5

In Example 1, it was carried out in the same manner as in Example 1, except that 4.3 mmol of the compound represented by the following Formula 1-5 was substituted for the compound represented by the Formula 1-1.

[Formula 1-5]

Comparative Example 1

In Example 1, it was carried out in the same manner as in Example 1, except that the compound represented by Formula 1-1 was not added.

Comparative Example 2

In Example 1, it was carried out in the same manner as in Example 1, except that 4.3 mmol of the compound represented by Formula 2 instead of the compound represented by Formula 1-1 was added.

[Formula 2]

Experimental Example

Experimental Example 1

For each modified or unmodified conjugated diene-based polymer prepared in the above Examples and Comparative Examples, weight average molecular weight (Mw, X10 ³ g / mol), number average molecular weight (Mn, X10 ³ g / mol), and molecular weight distribution ( MWD) and fringe viscosity (MV) were measured, respectively. The results are shown in Table 1 below.

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation chromatohraph) analysis, and the molecular weight distribution (MWD, Mw / Mn) was obtained by calculating from each of the measured molecular weights. Specifically, the GPC is a combination of two PLgel Olexis (Polymer Laboratories Co.) columns and one PLgel mixed-C (Polymer Laboratories Co.) column, and all newly replaced columns use a mixed bed type column. When calculating the molecular weight, the GPC standard material was performed using PS (polystyrene).

The pattern viscosity (MV, (ML1 + 4, @ 100 ℃) MU) was measured using Rotor Speed 2 ± 0.02 rpm, Large Rotorfmf at 100 ℃ using MV-2000 (ALPHA Technologies 社), and the sample used at this time Was left at room temperature (23 ± 3 ° C) for 30 minutes or more, and then 27 ± 3 g was collected, placed inside the die cavity, and platen was operated to measure for 4 minutes.

division Example Comparative example One 2 3 4 5 One 2 Mw (X10 ³ g / mol) 633 732 761 735 747 346 720 Mn (X10 ³ g / mol) 359 428 448 423 439 243 433 MWD (Mw / Mn) 1.76 1.71 1.70 1.74 1.67 1.42 1.66 MV 42 88 93 89 90 50 90

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition comprising each modified or unmodified conjugated diene-based copolymer prepared in the above Examples and Comparative Examples and the molded article prepared therefrom, tensile properties, abrasion resistance and wet road resistance were measured respectively. The results are shown in Table 3 below.

1) Preparation of rubber specimen

Each modified or unmodified conjugated diene-based polymer of Examples and Comparative Examples was blended under the mixing conditions shown in Table 2 below as a raw material rubber. The raw materials in Table 2 are each part by weight based on 100 parts by weight of rubber.

division Raw material Content (parts by weight) First stage kneading Rubber (including 37.5 parts by weight of process oil) 137.5 Silica 70.0 Coupling agent 11.2 Zinc agent 3.0 Stearic acid 2.0 Antioxidant 2.0 Antioxidant 2.0 Wax 1.0 Rubber accelerator 1.75 2nd stage kneading sulfur 1.5 Vulcanization accelerator 2.0

Specifically, the rubber specimen is kneaded through first stage kneading and second stage kneading. In the first stage kneading, raw rubber (conjugated diene-based polymer), filler, organosilane coupling agent, process oil, zincation, stearic acid, antioxidant, anti-aging agent, wax and accelerator are used by using a Banbari mixer equipped with a temperature control device. Kneaded. At this time, the temperature of the kneader was controlled, and a primary blend was obtained at a discharge temperature of 145 ° C to 155 ° C. In the second-stage kneading, after the primary formulation was cooled to room temperature, the primary formulation, sulfur, and a vulcanization accelerator were added to the kneader, followed by mixing at a temperature of 100 ° C. or lower to obtain a secondary formulation. Thereafter, a rubber specimen was prepared through a curing process at 100 ° C. for 20 minutes.

2) Tensile properties

Tensile properties were prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting of the test piece and the tensile stress at 300% elongation (300% modulus) were measured. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron Corporation) tensile tester.

3) Wear resistance

Using an Akron abrasion tester, the wear amount at a load of 6 pounds and 1000 revolutions was measured and indexed. The smaller the index value, the better the wear resistance.

4) Viscoelastic properties

The viscoelastic property was measured by changing the strain at a frequency of 10 Hz and at each measurement temperature (-60 ° C to 60 ° C) in a torsion mode using a dynamic mechanical analyzer (TA). The Payne effect was expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain. The higher the low temperature 0 ° C tan δ, the better the wet road resistance, and the lower the high temperature 60 ° C tan δ, the less hysteresis loss and excellent low running resistance (fuel efficiency).

division Example Comparative example One 2 3 4 5 One 2 Tensile properties 300% modulus (kgf / cm ² ) 132 122 130 117 120 85 105 Tensile strength (kgf / cm ² ) 213 193 202 187 197 151 177 Abrasion resistance 119 120 122 137 130 161 141 Viscoelastic tan δ @ 0 ℃ 0.977 0.915 0.901 0.917 0.911 0.637 0.866 tan δ @ 60 ℃ 0.101 0.106 0.110 0.119 0.107 0.143 0.110

As shown in Table 3, it was confirmed that the modified conjugated diene-based polymer according to the present invention exhibited significantly improved tensile properties, abrasion resistance, and viscoelastic properties compared to Comparative Example 1 in which the modification reaction was not performed. In addition, the modified conjugated diene-based polymer according to the present invention includes a substituent derived from imidazole by including a functional group derived from a modifier containing a substituent derived from pyrrole, pyrrolidine, or piperazine at one end of the polymer. Compared to Comparative Example 2 containing a functional group derived from a denaturant, the tensile properties and abrasion resistance were significantly improved, and it was confirmed from the above results that the wet road resistance was also excellent.

Claims (12)

A modified conjugated diene-based polymer comprising a functional group derived from a modifier comprising a repeating unit derived from a conjugated diene-based monomer and a compound represented by the following Chemical Formula 1 at one end:
[Formula 1]

In Chemical Formula 1,
R ¹ is pyrrolidine unsubstituted or substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, pyrrole unsubstituted or substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or 1 to 1 to 10 carbon atoms. Is a piperazine substituted or unsubstituted with a hydrocarbon group,
R ² and R ³ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ , R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms,
m is an integer of 1 or 2, n is an integer selected from 1 to 3. According to claim 1,
In Chemical Formula 1,
R ¹ is a pyrrolidine substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, a pyrrole substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms, or substituted or unsubstituted with an alkyl group having 1 to 5 carbon atoms. A substituted piperazine, wherein the N atom of pyrrolidine, pyrrole, or piperazine is bonded to R ² ,
R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms,
R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
m is an integer of 1 or 2, n is an integer selected from 1 to 3, modified conjugated diene-based polymer. According to claim 1,
The compound represented by Formula 1 is at least one modified conjugated diene-based polymer selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-5.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In the above formulas 1-1 to 1-5, Et is an ethyl group. According to claim 1,
The modified conjugated diene-based polymer further comprises a repeating unit derived from an aromatic vinyl monomer. According to claim 1,
The modified conjugated diene-based polymer is a modified conjugated diene-based polymer having a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol. According to claim 1,
The modified conjugated diene-based polymer is a modified conjugated diene-based polymer having a molecular weight distribution (Mw / Mn) of 1 to 5. In a hydrocarbon solvent containing an organometallic compound, a step of polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer to prepare an active polymer in which an organic metal is bound (S1); And
Method for producing a modified conjugated diene-based polymer comprising the step (S2) of reacting with a modifier containing the active polymer and a compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ¹ is pyrrolidine unsubstituted or substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, pyrrole unsubstituted or substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or 1 to 1 to 10 carbon atoms. Is a piperazine substituted or unsubstituted with a hydrocarbon group,
R ² and R ³ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ , R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms,
m is an integer of 1 or 2, n is an integer selected from 1 to 3. The method of claim 7,
The organometallic compound is a method of preparing a modified conjugated diene polymer, which is used in an amount of 0.01 mmol to 10 mmol based on 100 g of monomers. The method of claim 7,
The organometallic compound is methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium , n-ethylsilicium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium Method for producing a modified conjugated diene polymer having at least one selected from the group consisting of alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide . The method of claim 7,
The polymerization of the step (S1) is a modified conjugated diene-based polymer production method that is carried out by including a polar additive. The method of claim 10,
The polar additives are tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-Dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine at least one selected from the group consisting of modified conjugated diene-based polymer production method. Modifier comprising a compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
R ¹ is pyrrolidine unsubstituted or substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, pyrrole unsubstituted or substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Is a piperazine substituted or unsubstituted with a hydrocarbon group,
R ² and R ³ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ , R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms,
m is an integer of 1 or 2, n is an integer selected from 1 to 3.