KR20150037671A - Modified diene polymer, a method of making the same and a rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a modified conjugated diene-based polymer, comprising the steps of: polymerizing a conjugated diene-based monomer separately or polymerizing the same with an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound, and forming an active polymer having an alkali metal terminal; and reacting the active polymer having the alkali metal terminal with an aromatic compound having an epoxy group, and reacting the same with an isocyanate compound having an alkoxysilyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to a modified conjugated diene polymer, a process for producing the modified conjugated diene polymer, and a rubber composition comprising the modified conjugated diene polymer,

The present invention relates to a modified conjugated diene polymer, a process for producing the modified conjugated diene polymer, and a rubber composition containing the modified conjugated diene polymer. More particularly, the present invention relates to a modified conjugated diene polymer which is obtained by sequentially modifying a conjugated diene polymer by using a compound having a predetermined epoxy group and then an isocyanate compound having an alkoxysilyl group And a modified conjugated diene polymer produced thereby, and a rubber composition comprising the modified conjugated diene polymer and having excellent heat resistance, tensile strength, abrasion resistance, and wet road surface resistance.

[0002] In recent years, due to environmental problems and resource problems, vehicle fuel tires are required to have a low fuel consumption ratio, and excellent heat resistance, tensile strength, abrasion resistance and wet road surface resistance are demanded from the viewpoint of safety.

As a method of improving the rubber composition for a tire, there are a method of improving the raw material rubber such as butadiene rubber or styrene-butadiene rubber, a method of improving the structure and the composition of the reinforcing filler such as silica or black carbon, the hardener and the plasticizer.

As one of such methods, there have been proposed various methods of modifying the active terminal of the conjugated diene polymer or the active terminal of the conjugated diene-based copolymer with a modifying agent, but the physical properties of the rubber made from such a conjugated diene polymer / There is room for improvement.

KR 2013-0090811 A

The present invention relates to a rubber composition capable of providing a rubber having improved exothermicity, tensile strength, abrasion resistance and wet road surface resistance, including a modified conjugated diene polymer and a modified conjugated diene polymer, and a process for producing the rubber composition do.

According to one aspect of the present invention, there is provided a process for producing an active polymer having an alkali metal terminal by polymerizing a conjugated diene monomer alone or with an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound ; And reacting the active polymer having an alkali metal terminal with an aromatic compound having an epoxy group (first compound) and then reacting with an isocyanate compound having an alkoxysilyl group (second compound), to obtain a modified conjugated diene polymer A manufacturing method is provided.

Non-limiting examples of the aromatic compound (first compound) having an epoxy group that can be used in the present invention include n, n, n ', n'-tetrakis (oxiranylmethyl) -1,3-benzene dimethanamine, diglycidyl Diglycidylbenzene, 1,3,5-triglycidylbenzene, 4,4'-diglycidyl-diphenylmethylamine, 4,4'-diglycidyl - dibenzylmethylamine. Preferably, n, n, n ', n'-tetrakis (oxiranylmethyl) -1,3-benzenedimethanamine represented by the following general formula (1) can be given.

Non-limiting examples of the isocyanate compound (second compound) having an alkoxysilyl group usable in the present invention include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- 3-isocyanatopropyltriisopropoxysilane, and the like, preferably 3-isocyanatopropyltriethoxysilane represented by the following formula (2).

According to another aspect of the present invention, there is provided a modified conjugated diene polymer obtained by the above production method.

According to still another aspect of the present invention, there is provided a rubber composition comprising the modified conjugated diene polymer.

The rubber produced using the modified conjugated diene polymer according to the present invention has excellent tensile strength, abrasion resistance, and wet road surface resistance in addition to excellent heat generation.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The modified conjugated diene polymer of the present invention is obtained by polymerizing a conjugated diene monomer alone or with an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And reacting the active polymer having an alkali metal terminal with an aromatic compound having an epoxy group (first compound), and then reacting with an isocyanate compound having an alkoxysilyl group (second compound).

As used herein, the term " polymer " is understood to be used in a broad sense including a copolymer, unless it is referred to as a " homopolymer ".

The aromatic compound having an epoxy group in the present specification is used in the same meaning as the term 'first compound', and the isocyanate compound having an alkoxysilyl group has the same meaning as the term 'second compound'.

The active polymer having an alkali metal terminal may be formed from a homopolymer of a conjugated diene monomer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer. That is, the active polymer having an alkali metal terminal may be composed of 50 to 100% by weight of a conjugated diene monomer unit and 50 to 0% by weight of an aromatic vinyl monomer unit.

Non-limiting examples of conjugated diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, , 1,3-pentadiene, and the like. Of these, 1,3-butadiene and isoprene (2-methyl-1,3-butadiene) are preferred. These may be used alone or in combination of two or more.

Non-limiting examples of aromatic vinyl monomers include styrene,? -Methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4- diisopropylstyrene, -Butyl styrene, 5-t-butyl-2-methylstyrene, 4-t-butoxystyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, dimethylaminomethylstyrene and dimethylaminoethylstyrene. These may be used alone or in combination of two or more.

The bonding mode of the conjugated dienic monomer and the aromatic vinyl monomer can be in various bonding modes such as block, taper, and random, and is not particularly limited.

In addition to the conjugated diene monomer and the aromatic vinyl monomer, other monomers may be contained within a range that does not substantially interfere with the effect of the present invention. Non-limiting examples of other monomers include ethylenically unsaturated carboxylic acid ester monomers such as isopropyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate; Olefin monomers such as ethylene, propylene, isobutylene and vinyl cyclohexane; And non-conjugated diene monomers such as 1,4-pentane diene and 1,4-hexane diene.

Non-limiting examples of the organic alkali metal compound that provides the alkali metal at the end of the active polymer include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, ; Organic polyvalent lithium compounds such as 1,4-dichlorobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-tritylobenzene; Organic sodium compounds such as sodium naphthalene; And an organic potassium compound such as potassium naphthalene. Of these, organic lithium compounds, particularly organic monolithium compounds, are preferred. These alkali metals may be used alone or in combination of two or more.

Since the modified conjugated diene polymer of the present invention is prepared by solution polymerization, the solvent that can be used in the present invention is inert and should not inhibit the solution polymerization reaction. The solvent is not particularly limited as long as it is an inert solvent which is usually used in solution polymerization and does not inhibit the solution polymerization reaction. Non-limiting examples include aliphatic hydrocarbons such as butane, pentane, hexane, and 2-butene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclohexene; And aromatic hydrocarbons such as benzene, toluene and xylene. The solvent is used in an amount such that the monomer concentration is 1 to 50 wt% or 10 to 40 wt%.

During the polymerization reaction, a polar compound may be added to bring the vinyl bond to a desired level. Examples of the polar compound include ether compounds such as dibutyl ether and tetrahydrofuran; Tertiary amines such as tetramethylethylenediamine; And alkali metal alkoxides; Phosphine compounds and the like. Among them, ether compounds and tertiary amines are preferably used, tertiary amines are more preferably used, and tetramethylethylenediamine is particularly preferably used. The amount of the polar compound to be used is preferably 0.01 to 100 moles, more preferably 0.3 to 30 moles, per 1 mole of the alkali metal. When the amount of the polar compound used is within the above range, the amount of vinyl bond in the conjugated diene monomer can be easily controlled and the problem of catalyst deactivation does not occur.

The polymerization temperature is usually -78 to 150 캜, preferably 0 to 100 캜, more preferably 30 to 90 캜. The polymerization can be carried out, for example, in a batch or continuous manner.

Then, an active polymer having an alkali metal terminal is reacted with an aromatic compound having an epoxy group (first compound).

Non-limiting examples of the aromatic compound (first compound) having an epoxy group usable in the present invention include non-limiting examples of the aromatic compound (first compound) having an epoxy group usable in the present invention include n, n, n ', n -Tetrakis (oxiranylmethyl) -1,3-benzene dimethanamine, diglycidyl bisphenol A, 1,4-diglycidyl benzene, 1,3,5-triglycidyl benzene, 4,4 '-Diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine. Preferably, n, n, n ', n'-tetrakis (oxiranylmethyl) -1,3-benzenedimethanamine represented by the following general formula (1) can be given.

[Chemical Formula 1]

The aromatic compound (first compound) having an epoxy group is used in an amount of 0.01 to 10 mol, preferably 0.1 to 1 mol, more preferably 0.1 to 0.5 mol, per 1 mol of the alkali metal used in the polymerization.

The reaction of the active polymer with the compound of formula (I) can be carried out usually at a reaction temperature of 0 to 100 ° C, preferably 30 to 90 ° C, for 1 to 120 minutes, preferably 2 to 60 minutes.

Then, the conjugated diene-based copolymer modified with an aromatic compound (first compound) is reacted with an isocyanate compound (second compound) having an alkoxysilyl group.

Non-limiting examples of the isocyanate compound (second compound) having an alkoxysilyl group usable in the present invention include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- 3-isocyanatopropyltriisopropoxysilane, and the like, preferably 3-isocyanatopropyltriethoxysilane represented by the following formula (2).

(2)

The isocyanate compound (second compound) having an alkoxysilyl group is used in an amount of 0.01 to 10 mol, preferably 0.1 to 1 mol, more preferably 0.1 to 0.5 mol, based on 1 mol of the alkali metal used in the polymerization.

The reaction of the second compound with the active polymer modified by the first compound is usually carried out at a reaction temperature of 0 to 100 캜, preferably 30 to 90 캜, usually for 1 to 120 minutes, preferably 2 to 60 minutes .

The first compound and the second compound are dissolved in an inert solvent used in polymerization and added to the polymerization system.

The reaction can be stopped by adding an alcohol such as methanol, isopropanol or water as a polymerization terminator.

Subsequently, an antioxidant, a columnarizing agent, an anti-scale agent or the like is added to the polymerization solution as required, and the polymerization solvent is separated from the polymerization solution by direct drying or steam stripping to recover the intended modified conjugated diene polymer.

The modified conjugated diene-based polymer may have a block form, a branched form or a multilayered form.

The Mooney viscosity (ML _{1 +4} ) of the modified conjugated diene-based polymer rubber is preferably 10 to 200, more preferably 20 to 150. If the viscosity is less than 10, the mechanical properties such as the tensile strength of the vulcanized rubber may decrease. If the viscosity exceeds 200, mixing with other components such as other rubbers, which may be difficult to produce the rubber composition, may result in very poor miscibility if the modified polymer rubber is used as a component of the rubber composition, The mechanical properties of the vulcanized rubber composition may be deteriorated.

The content of the vinyl bond derived from the conjugated diene monomer and contained in the obtained modified conjugated diene-based polymer rubber is preferably 10 to 70% by weight, more preferably 15 to 60% by weight. If the content is less than 10% by weight, the glass transition temperature of the modified polymer rubber may be lowered, and the grip performance of the tire containing the modified polymer rubber may be deteriorated. When the content is more than 70% by weight, the glass transition temperature of the modified polymer rubber may be increased, and the impact resistance of the modified polymer rubber may be lowered.

In one aspect of the present invention, there is provided a rubber composition comprising the modified conjugated diene-based polymer.

The rubber composition may contain other rubbers in addition to the modified conjugated diene polymer of the present invention. Examples of other rubbers include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, solution-polymerized styrene-butadiene copolymer rubber, and high-trans rubber having a trans-bond content in the 1,3- Styrene-butadiene copolymer rubber, styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polybutadiene rubber or polybutadiene rubber having a low sheath bond content, polybutadiene rubber having a low sheath bond content, Nitrile-butadiene copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, acrylic rubber, epichlorohydrin rubber, fluorine rubber, silicon rubber, ethylene-propylene rubber and urethane rubber. Among them, natural rubber, polyisoprene rubber, polybutadiene rubber and styrene-butadiene copolymer rubber are preferably used. These rubbers may be used alone or in combination of two or more.

When the modified conjugated diene polymer of the present invention is used together with other rubber, the proportion of the modified conjugated diene polymer of the present invention is preferably 10% by weight or more, or 20 to 95% by weight based on the total weight of the rubber do. If the content of the modified conjugated diene polymer according to the present invention is too small, the physical properties of the rubber composition may be deteriorated.

The rubber composition of the present invention may contain silica. Non-limiting examples of the silica include dry type white carbon, wet type white carbon, colloidal silica, precipitated silica and the like. Also, a carbon-silica dual-phase filler in which silica is supported on the surface of carbon black may be used. These silicas may be used alone or in combination of two or more. The nitrogen adsorption specific surface area (measured by the BET method according to ASTM D3037-81) of silica is preferably 50 to 400 m2 / g, more preferably 100 to 220 m2 / g. In this range, abrasion resistance and low heat generation are more excellent. The blending amount of silica is preferably 10 to 150 parts by weight, more preferably 20 to 120 parts by weight, particularly preferably 40 to 100 parts by weight, based on 100 parts by weight of the total rubber.

When silica is compounded, addition of a silane coupling agent can further improve low heat build-up and wear resistance. Non-limiting examples of the silane coupling agent include vinyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (? -Aminoethyl) -? - aminopropyltrimethoxysilane , Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, gamma -trimethoxysilylpropyldimethylthiocarbamate tetrasulfide, Methoxysilylpropyl benzothiazyl tetrasulfide, and the like. Among them, a silane coupling agent having a tetra sulfide structure is preferable. These silane coupling agents may be used alone or in combination of two or more. The blending amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight based on 100 parts by weight of silica.

In addition, carbon blacks such as Fanes black, acetylene black, thermal black, channel black, graphite, graphite fiber and fullerene can be incorporated into the rubber composition. Among them, Fanes black is preferable, and examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, ISAF-HS, HAF, HAF-HA, HAF-LS and FEF. These carbon blacks may be used alone or in combination of two or more.

In addition to the above components, a compounding agent such as a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an antioxidant, an activator, a process oil, a plasticizer, a lubricant and a filler may be added to the rubber composition according to a conventional method.

Examples of the crosslinking agent include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly disperse sulfur; Sulfur halides such as sulfur monochloride and sulfur dichloride; Organic peroxides such as dicumyl peroxide and ditaclylobutyl peroxide; quinonedioxime such as p-quinonedioxime and p, p'-dibenzoylquinone dioxime; Organic polyamine compounds such as triethylenetetramine, hexamethylenediamine carbamate and 4,4'-methylenebis-o-chloroaniline; An alkylphenol resin having a methylol group; Among them, sulfur is preferable, and powdered sulfur is more preferable. These crosslinking agents may be used alone or in combination of two or more.

The blending amount of the crosslinking agent is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total rubber.

Examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene- Sulfenamide-based crosslinking accelerators such as benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; Guanidine-based cross-linking accelerators such as diphenylguanidine, diorthotolylguanidine, and orthotolubiguanidine; Thiourea-based crosslinking accelerators such as diethylthiourea; Thiol-based crosslinking accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and 2-mercaptobenzothiazole; Thiuram-based crosslinking accelerators such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Dithiocarbamate-based cross-linking accelerators such as sodium dimethyldithiocarbamate and zinc diethyldithiocarbamate; Xanthogen acid-based cross-linking accelerators such as sodium isopropyl xanthogenate, zinc isopropyl xanthogenate, zinc butyl xanthogenate, and the like; And the like. Among them, it is particularly preferable to include a sulfenamide-based crosslinking accelerator. These crosslinking accelerators may be used alone or in combination of two or more.

The blending amount of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total rubber.

As the crosslinking activator, for example, higher fatty acids such as stearic acid and zinc oxide can be used. The zinc oxide preferably has a particle size of not more than 5 mu m with a high surface activity, for example, active zincation with a particle size of 0.05 to 0.2 mu m, zincification with 0.3 to 1 mu m, and the like. As the zinc oxide, an amine-based dispersing agent or a surface treated with a wetting agent may be used.

The blending amount of the crosslinking activator is appropriately selected. The blending amount of the higher fatty acid is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total rubber, Is preferably from 0.05 to 10 parts by weight, more preferably from 0.5 to 3 parts by weight, based on 100 parts by weight.

The process oil may be mineral oil or synthetic oil. As mineral oil, aroma oil, naphthenic oil, paraffin oil and the like are usually used. Other mixing agents include diethylene glycol, polyethylene glycol, and silicone oil; Fillers such as calcium carbonate, talc, and clay; A tackifier such as petroleum resin, coumarone resin and the like; Wax and the like. For example, a rubber composition may be obtained by kneading a compounding agent other than a crosslinking agent and a crosslinking accelerator with a dielectric rubber, and then mixing the crosslinking agent and the crosslinking accelerator with the kneaded product.

The kneading temperature of the compounding agent and the dielectric rubber excluding the crosslinking agent and the crosslinking accelerator is preferably 80 to 200 占 폚, more preferably 120 to 180 占 폚, and the kneading time is preferably 30 seconds to 30 minutes.

The mixing of the crosslinking agent and the crosslinking accelerator is usually carried out after cooling to 100 DEG C or lower, preferably 80 DEG C or lower.

The rubber composition of the present invention is generally used by crosslinking. The crosslinking method is not particularly limited and may be selected depending on the shape, size, etc. of the crosslinked product. The rubber composition may be crosslinked at the same time as the molding by filling the rubber composition containing the crosslinking agent in the mold and heating it. Alternatively, the rubber composition containing the crosslinking agent may be molded in advance and then heated. The crosslinking temperature is preferably 120 to 200 占 폚, more preferably 140 to 180 占 폚, and the crosslinking time is usually about 1 to 120 minutes.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example  One

Three reactors were prepared. Of the three reactors, the first and second reactor were used as polymerization reactors, and the third reactor was used as a denaturing reactor.

Styrene, 1,3-butadiene and n-hexane from which impurities such as water were removed were preliminarily mixed at a rate of 2.373 kg / h, 3.921 kg / h and 4.196 kg / h, respectively, before entering the reactor. The resulting mixed solution was continuously fed into a first reactor, and then 2,2-bis (2-oxoranyl) propane and n-butyllithium were fed at a rate of 3.58 g / h and 39.57 mmol / h respectively To the first stage reactor and the internal temperature of the reactor was adjusted to 70 ° C.

The resultant polymer of the first reactor was continuously supplied to the upper portion of the reactor of the second reactor, and the polymerization reaction was continued at a temperature of 70 ° C. The resulting polymer of the second-stage reactor was continuously supplied to the upper portion of the tertiary reactor and 9.23 mmol / h of 1,3-phenylenebis [N, N-bis (oxiran-2-ylmethyl) methanamine, 9.23 mmol / h were successively supplied and the denaturation reaction proceeded. The polymerization reaction was stopped by adding a solution of isopropyl alcohol and an antioxidant (Wingstay-K) in a ratio of 8: 2 to the resultant polymer of the third-stage reactor at a rate of 32.5 g / h to obtain a polymer.

To 100 parts by weight of the polymer, 37.5 phr of TDAE oil (treated distilled aromatic extract having a glass transition temperature in the range of about -44 to about -50 ° C) was added, and the mixture was stirred in hot water heated with steam to remove the solvent, Followed by roll drying to remove the remaining solvent and water to prepare a modified conjugated diene polymer. The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 1 below.

Comparative Example  One

Modified conjugated diene polymer was prepared in the same manner as in Example 1 except that 9.23 mmol / h of 1,3-phenylenebis [N, N-bis (oxiran-2-ylmethyl) methanamine was supplied as a modifier.

Comparative Example  2

The analytical results of the commercially available modified conjugated diene polymer (TUFDENETM 3835, manufactured by Asahi Kasei) are shown in Table 1 below. For reference, RAE oil was used instead of the TDAE oil used in Example 1 for the unmodified conjugated diene polymer (TUFDENETM 3835).

The analysis of the conjugated diene polymer prepared in Example 1 and Comparative Examples 1 and 2 was carried out by the following method.

Mooney Viscosity: 2 pieces of specimen weighing more than 15 g were preheated for one minute using MV-2000 manufactured by ALPHA Technologies and then measured at 100 ° C for 4 minutes.

B) Content of styrene monomer (SM) and vinyl (Vinyl): measured by NMR.

C) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (PDI): measured by GPC analysis under the condition of 40 캜. In this case, two columns of PLgel Olexis column manufactured by Polymer Laboratories were combined with one column of PLgel mixed-C column, and all of the new columns were of mixed bed type. Also, PS (Polystyrene) was used as a GPC reference material in molecular weight calculation.

division Example Comparative Example One One 2 sample A B C n-butyllithium (mmol / h) 39.57 39.57 39.57 Polarity additive (g / h) 3.58 3.58 3.58 Denaturant
(mmol / h) a * 9.23 9.23 - b * 9.23 - - TDAE oil (phr) 37.5 37.5 RAE (37.5) Mooney viscosity (MV) 73 72 53 NMR (%) SM 36 36 36 Vinyl 26 26 26 GPC (x 10 ⁴ ) Mn 58 58 33 Mw 136 136 94 PDI 2.3 2.3 2.0

a *: 1,3-Phenylenebis [N, N-bis (oxiran-2-ylmethyl) methanamine

b *: 3-Isocyanatopropyltriehoxysilane

C: TUFDENETM 3835, manufactured by Asahi Kasei

The conjugated diene-based polymer rubber composition was prepared by using each of A, B, and C in the samples shown in Table 1 as the raw rubber under the mixing conditions shown in Table 2 below. The raw materials in Table 2 are based on 100 parts by weight of rubber.

As a concrete method of kneading the rubber composition of the conjugated diene polymer, a Banbury mixer equipped with a temperature controller is used. In the kneading of the first stage, a raw rubber (conjugated diene polymer), a filler, an organic silane coupling agent, Zinc stearate, stearic acid antioxidant, antioxidant, wax and accelerator were kneaded. At this time, the temperature of the kneader was controlled and a primary blend was obtained at an outlet temperature of 145 to 155 占 폚. As the kneading in the second stage, the primary blend was cooled to room temperature, rubber, sulfur and a vulcanization accelerator were added to the kneader, followed by mixing at a temperature of 100 DEG C or lower to obtain a second blend. Finally, the cured product was subjected to a curing process at 100 ° C for 20 minutes to obtain a conjugated diene-based polymer of Production Example 1 using the polymer of Example 1 as a raw material rubber and Comparative Production Examples 1 and 2 using the polymer of Comparative Examples 1 and 2 as a raw rubber A rubber composition was prepared.

division matter Content (unit: phr) First stage kneading Rubber 137.5 Silica 70.0 Coupling agent 11.2 oil - Zinc 3.0 Stearic acid 2.0 Antioxidant 2.0 Antioxidant 2.0 Wax 1.0 Second stage kneading Rubber accelerator 1.75 sulfur 1.5 Vulcanization accelerator 2.0 Gross weight 234.0

The physical properties of each prepared vulcanized rubber were measured by the following methods.

1) Tensile test

The tensile strength at the time of cutting of the test piece and the tensile stress at 300% elongation (300% modulus) were measured by the tensile test method of ASTM 412. For this purpose, Universal Testing Machine 4204 tensile tester from Instron was used. Tensile strength, modulus and elongation were measured at room temperature with a tensile speed of 50 cm / min.

2) Viscoelastic properties

A dynamic mechanical analyzer from TA Corporation was used. Tan δ was measured by changing the strain at a frequency of 10 Hz and a measurement temperature (-60 to 60 ° C.) in a twist mode. The Pheny effect was expressed as the difference between the minimum value and the maximum value at 0.28% to 40% of the strain. The smaller the fines effect, the better the dispersibility of fillers such as silica. Higher temperature at 0 캜 Tan δ has a better wet road surface resistance. The lower tan δ at 60 캜 has a lower hysteresis loss and a lower rolling resistance of the tire, that is, an excellent low fuel consumption. The physical properties of the vulcanized rubber are shown in Table 3 below.

division Test Example 1 Test Example 2 Test Example 3 sample Production Example 1 Comparative Preparation Example 1 Comparative Production Example 2 300% modulus
(Kgf / cm2) 135 125 110 The tensile strength
(Kgf / cm2) 204 193 177 Tan δ at 0 ° C 0.883 0.815 0.792 Tan δ at 60 ° C 0.070 0.108 0.142 60 ° C ΔG '(Pheny effect) 0.35 0.40 0.45

As shown in the results of Table 3, the modified conjugated diene polymer rubber composition of Example 1 according to the present invention showed a significant improvement of 300% modulus (tensile stress) and tensile strength compared with Comparative Examples 1 and 2, Also, when the Tan δ value at 60 ° C was low and the modified conjugated diene polymer of the present invention was included in the tire, the rolling resistance was lower than that of the prior art and it was confirmed that the fuel efficiency was good.

Further, in the case of the modified conjugated diene polymer of Example 1 according to the present invention, Tan δ values at 0 캜 were higher than those of Comparative Examples 1 and 2, and the modified conjugated diene polymer of the present invention It was confirmed that the resistance on the wet road surface was high.

In addition, it was confirmed that the modified conjugated diene rubber copolymer of Example 1 according to the present invention had a lower ΔG 'value at 60 ° C. than Comparative Examples 1 and 2, thereby improving the dispersion degree of silica.

Claims (11)

Polymerizing the conjugated diene monomer alone or in an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to form an active polymer having an alkali metal terminal; And
Reacting an active polymer having an alkali metal terminal with an aromatic compound having an epoxy group and subsequently reacting with an isocyanate compound having an alkoxysilyl group. The method according to claim 1,
The aromatic compound having an epoxy group is preferably an aromatic compound having an epoxy group such as n, n, n ', n'-tetrakis (oxiranylmethyl) -1,3-benzenedimethanamine, diglycidylbisphenol A, , 1,3,5-triglycidylbenzene, 4,4'-diglycidyl-diphenylmethylamine, and 4,4'-diglycidyl-dibenzylmethylamine. Wherein the mixture is a mixture of two or more kinds of monomers. The method according to claim 1,
Wherein the aromatic compound having an epoxy group is n, n, n ', n'-tetrakis (oxiranylmethyl) -1,3-benzenedimethanamine. The method according to claim 1,
Wherein the aromatic compound having an epoxy group is used in an amount of 0.01 to 10 mol based on 1 mol of the organic alkali metal compound, The method according to claim 1,
The alkoxysilyl group-containing isocyanate compound is preferably selected from the group consisting of 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane and 3-isocyanato Propyltrimethoxysilane, propyltrimethoxysilane, propyltriisopropoxysilane, and mixtures thereof. 2. The method of producing a modified conjugated diene-based polymer according to claim 1, The method according to claim 1,
Wherein the isocyanate compound having an alkoxysilyl group is 3-isocyanatopropyltriethoxysilane. 2. The process for producing a modified conjugated diene-based polymer according to claim 1, The method according to claim 1,
Wherein the isocyanate compound having an alkoxysilyl group is used in an amount of 0.01 to 10 moles per mole of the organic alkali metal compound. The method according to claim 1,
Wherein the organic alkali metal compound is selected from the group consisting of n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-tritylobenzene; Sodium naphthalene compounds; And potassium naphthalene. 2. The method for producing a modified conjugated diene-based polymer according to claim 1, The method according to claim 1,
The conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl- - < / RTI > pentadiene, and mixtures of two or more thereof. A modified conjugated diene polymer produced by the production method according to any one of claims 1 to 9. A rubber composition comprising the modified conjugated diene polymer according to claim 10.