WO2016104986A1 - Modified conjugated diene-based polymer and composition containing same - Google Patents

Abstract

The present invention provides a modified diene-based polymer in which a functional monomer for converting an ester group into carboxylic acid or anhydride under heat or an acid catalyst is introduced to an end of a vinyl aromatic-conjugated diene-based copolymer, thereby enhancing compatibility and binding force with a hydroxyl group on a surface of an inorganic filler, leading to excellent affinity to the inorganic filler. The application of the modified conjugated diene-based copolymer, according to the present invention, to a tire material improves affinity with in the inorganic filler, thereby obtaining a low hysteresis loss, excellent wet skid balance, and favorable storage stability, which are characteristics required for a tire.

Description

Modified conjugated diene-based polymer and composition comprising the same

The present invention relates to a modified conjugated diene-based polymer and a composition comprising the same, and more particularly, at least one of the start end and the end end of the polymer chain are hydrolyzed under a heat or acid catalyst so that the ester group is carboxyl group or anhydride. The present invention relates to a modified conjugated diene-based polymer having excellent storage stability and excellent affinity with a polar inorganic additive such as silica, and a composition comprising the same.

Recently, with increasing interest in eco-friendly materials and energy-saving materials, modified conjugated diene-based polymer materials incorporating functional chemicals into diene-based polymers have been used in various applications. In particular, the application of such modified conjugated diene-based polymers to automobile tires is increasing the demand for the development of material technology that can improve braking performance and fuel economy. Conventionally, styrene-butadiene rubber (ESBR) obtained from emulsion polymerization is used as a material used for tire tread, and an additive such as carbon black and sulfur, which are inorganic additives, is used for blending and vulcanizing to increase elastic modulus. However, in the case of ESBR material, it is difficult to control the molecular weight and molecular weight distribution during the polymerization process, and also has limitations in controlling the microstructure of the polymer.

On the other hand, in the case of styrene butadiene rubber (SSBR) obtained by solution polymerization, an organometallic catalyst such as butyl lithium having carbon anionicity is generally used as an initiator, and the molecular weight and molecular weight distribution are characteristic of the polymerization method called anion polymerization. Of course, not only the polymer micro-structure but also the macro-structure can be freely controlled, so that it is possible to design a rubber material that can improve braking performance and reduce fuel consumption when used in a tire tread. Here, in order to further improve performance, the use of inorganic particles having a polar group to chemically interact with the surface of particles such as silica instead of carbon black is increasing, and functional groups capable of binding or interacting with these inorganic particles to the polymer ends. It is known that tire performance can be improved further by using the modified conjugated diene type polymer which introduce | transduced.

However, in the case of styrene-butadiene rubber obtained through solution polymerization, in general, when mixed with fillers such as inorganic particles or metal oxide particles, the compatibility is poor, so that the dispersibility of the filler particles is lowered, thereby not only lowering physical properties. When applied as a tire material after vulcanization, the tire performance is reduced.

US Pat. No. 7,279,531 discloses a method of improving the dispersibility and affinity for carbon black by introducing a tin (Sn) -based compound into a conjugated diene-based polymer as a modified compound. However, there is a limit to effectively improving the binding and dispersibility with an inorganic additive such as silica having a polar group on the surface.

In US Pat. No. 7,335,706, hexachlorodisiloxane was used as a modified compound to increase the compatibility with silica. When the modified conjugated diene-based polymer prepared by using the compound is mixed with silica, fuel economy may be increased compared to the conjugated diene-based polymer which is not modified by the combination of silica, but due to strong toxicity, there is a limit to the production. However, the dispersion of silica is not sufficient and there is a limit in improving fuel efficiency when used in a tire.

In Japanese Patent Laid-Open No. 8-337614, an alkoxysilane containing a glycidyl group is used as a modified compound for compatibility with silica and strengthening bonds. When the modified conjugated diene-based polymer into which the compound is introduced is mixed with silica, fuel economy may be increased compared to the unmodified conjugated diene-based polymer.However, due to the coupling reaction between the alkoxysilane groups, the modified conjugated conjugate may be used for a long time after polymerization The pattern viscosity of the diene polymer may increase, and functional groups capable of bonding with the silica may be consumed by the coupling reaction, resulting in insufficient dispersion of the silica.

In Republic of Korea Patent Publication No. 10-2010-0078817, by using a coupling agent combined with methacrylate and polyethylene glycol to improve the affinity with silica to improve the braking and fuel efficiency on wet road surface, but the polyethylene glycol part Since the interaction between the ether group and the silanol group on the silica surface is not strong, the dispersion of silica may not be sufficient, and there is a limit to the improvement in running performance.

In US Pat. No. 6,365,668, carboxylic acid functional groups are introduced via post-reaction after polymerization of styrenebutadiene rubber. When the modified conjugated diene-based polymer is blended with silica, the running performance and braking performance may be improved compared to the unmodified conjugated diene-based polymer. However, in the long term, the peroxide added for the post-reaction reaction results in the use of styrenebutadiene rubber. There exists a possibility that the double bond of a 4-4-butadiene unit may decompose | disassemble and a running performance may fall.

The present invention has been made to solve the problems of the above-described prior arts, and an object of the present invention is to hydrolyze under a thermal or acid catalyst upon polymerization of a conjugated diene-based polymer so that an ester group is converted into a carboxyl group or anhydride. By introducing a functional monomer which can be used, the modified conjugated diene-based polymer having excellent affinity with polar inorganic additives is improved by blending with additives such as inorganic or metal oxide particles and the like.

Another object of the present invention is to provide a composition comprising the modified conjugated diene-based polymer of the present invention and an inorganic filler, the composition of the present invention improves the dispersibility of the inorganic additive and rubber, low hysteresis when applied to a tire material The balance between the loss property and the wet skid property, that is, the rotation resistance / braking property is excellent, and the storage stability is excellent.

In order to solve the above problems, the present invention includes a functional monomer in which at least one of the start end and end end of the polymer chain is hydrolyzed under a heat or acid catalyst to convert the ester group into a carboxyl group or anhydride. It provides a modified conjugated diene-based polymer.

In a preferred embodiment of the present invention, the functional monomer is a monomer represented by the following formula (1).

[Formula 1]

Here, R ₁ is hydrogen or an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ₂ is an alkyl group having 4 to 20 carbon atoms including a tertiary carbon, or an aryl group having 6 to 20 carbon atoms. Or an alkylsilyl group having 3 to 20 carbon atoms and 1 to 10 silicon atoms, or an arylsilyl group having 6 to 20 carbon atoms and 1 to 10 silicon atoms, and R ₂ is separated by a thermal or acid catalyst to obtain an ester of the monomer. The group is converted to a carboxylic acid group or an anhydride.

In Formula 1, preferred examples of R ₁ include hydrogen, methyl, ethyl, and the like, and preferred examples of R ₂ include tertiary-butyl ester group, trimethylsilyl ester group, triethylsilyl ester group, and tertiary-. A butoxyphenyl group, a trimethyl siloxy phenyl group, a triethyl siloxy phenyl group, etc. are mentioned.

The functional monomer is selected from the group selected from tert-butyl acrylate, tert-butyl methacrylate, trimethylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl acrylate and triethylsilyl methacrylate One or two or more compounds may be used, but the present invention is not limited thereto.

It is preferable that the modified conjugated diene type polymer of this invention contains the said functional monomer in the range of 1 or more and 100 or less in the terminal. In the case where the functional monomer is not introduced, the balance and storage stability of the low hysteresis loss and wet skid properties of the present invention are not improved, and when more than 100 of the functional monomers are introduced, the low fuel efficiency is not improved. Not.

In the modified conjugated diene-based polymer of the present invention, the functional monomer may be included in the polymer in an oligomeric block structure.

In the present invention, the conjugated diene polymer refers to a conjugated diene homopolymer obtained by polymerizing a diene monomer alone, or a conjugated diene copolymer obtained by copolymerizing two or more kinds of diene monomers, or a form different from a diene monomer. It may be a copolymer copolymerized together with a vinyl monomer of.

Accordingly, the modified conjugated diene-based polymer of the present invention may be subjected to (co) polymerization of one or more diene monomers or to copolymerization of diene monomers and vinyl aromatic monomers in the presence of an organometallic catalyst such as organolithium and a hydrocarbon solvent. At this time, the polymerization may be performed by adding the functional monomer to carry out the polymerization, and a polar additive may be further added as necessary during the polymerization.

Examples of the diene monomer include one or more selected from 1,3-butadiene and isoprene, but are not limited thereto.

Examples of the vinyl aromatic monomers include, but are not limited to, one or more selected from styrene and alpha methyl styrene.

The organometallic catalyst usable in the preparation of the modified conjugated diene-based polymer of the present invention is a form in which an alkali metal or an alkali earth metal is combined with a hydrocarbon anion, and examples of the alkali metal or alkali earth metal include lithium, sodium, potassium, and the like. May be, but is not limited to these. Preferred organometallic catalysts are organolithium catalysts, and non-limiting examples of organolithium catalysts include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium and isopropyllithium having one anion. , Octylithium, benzyllithium, phenyllithium, naphthyl lithium, and derivatives thereof, and one or a mixture of two or more thereof can be used. In addition, an organolithium catalyst having an anion may also be used, such as divinylbenzene lithium, dipropenylbenzene lithium, or lithium pyrollidide. It can be used as a species or mixture of 2 or more types. In some cases, one or more types of organolithium catalysts having one anion and organolithium catalysts having both anions may be used.

In the polymerization of the modified conjugated diene-based polymer of the present invention, in addition to the organometallic catalyst, a polar additive may be further used to control the microstructure of the polymer, to improve the polymerization rate, or to control the reactivity. The amount of added may vary depending on the purpose or type of the additive. Non-limiting examples of such polar additives include N, N, N ', N'-tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), diethyl ether, cycloamalether, dipropyl ether, ethylene glycol, tri Ethylamine, ethylbutyl ether, crown ether, ditetrahydrofurylpropane, ethyltetrahydrofuryl ether, triethylamine, and derivatives thereof. By such a polar additive, the random structure of the polymer and the contents of the vinyl group can be adjusted according to the purpose, and also improve the polymerization rate.

In the polymerization of the modified conjugated diene polymer of the present invention, usable hydrocarbon solvents include n-hexane, n-heptane, cyclohexane, isooctane, methylcyclopentane, benzene, toluene, xylene, and the like. It can mix and use 2 or more types. In the polymerization, the monomers are added to within 50% by weight in the hydrocarbon solvent, preferably at a level of 15 to 35% by weight. If the total content of the monomer exceeds 50% by weight, the viscosity of the solution rises, making it difficult to control the molecular weight or the heat of reaction or uniform stirring during the polymerization.

In the polymerization of the modified conjugated diene-based polymer of the present invention, the polymerization temperature may vary depending on the solvent, and in general, polymerization is possible at 10 to 160 ° C. The microstructure may vary depending on the polymerization temperature, and the polymerization temperature may be adjusted according to the purpose.

Although the coupling agent may be added at the time of superposition | polymerization of the modified conjugated diene type polymer of this invention, it is preferable to use what is two or more functional groups which can react with a living anion as said coupling agent. As the coupling agent, any one generally used in the art can be used, and when the functional group of the coupling agent is 2, a linear polymer obtained by doubling the molecular weight is obtained, and when the functional group of the coupling agent is 3 or more The star-polymer (star-polymer) can be obtained. Generally as the coupling agent, tin series, alkoxysilane series or halosilane series may be used, and a coupling agent containing a glycidyl group may be used. Non-limiting examples of coupling agents, tin-based coupling agents include diphenyltin dichloride, dibutyltin dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyl Tin trichloride, tetrachloro tin, tetra methoxytin, tetra ethoxytin, tetrapropoxytin and the like can be used, and the alkoxysilane series is dimethyldimethoxy silane, diethyldimethoxy silane, dipropyldimethoxysilane, di Butyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxy silane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrier Methoxysilane, tetramethoxysilane, tetraethoxysilane and the like can be used. The halosilane series is diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyl trichloro Rosilane, methyltrichlorosilane, tetrachlorosilane and the like can be used. Coupling agents containing glycidyl groups include 4,4'-methylenebis (N, N-diglycidylaniline), N, N-diglycidyl-4-glycidoxycyanine, N, N-di Glycidylaniline, N, N, N ', N'-tetraglycidyl-3,3'-diethyl-4,4'-diaminodiphenylmethane and the like can be used. The above-mentioned coupling agents may be used alone or in combination of two or more thereof. Illustrating the coupling agent is not intended to limit the structure, and any type can be used as long as it can react with active ends such as tin series, alkoxysilane series, halosilane series, glycidyl series.

In the modified conjugated diene-based polymer of the present invention, after the introduction of the functional monomer into the conjugated diene-based polymer, the conversion of the ester group of the functional monomer to carboxylic acid or anhydride through hydrolysis can be sufficiently hydrolyzed even through heat, but It is preferred to carry out under acid catalyst in order to induce hydrolysis more efficiently during the time. For this purpose, various acids such as hydrochloric acid, acetic acid, nitric acid and para-toluenesulfonic acid series may be applied.

The present invention also provides a composition comprising the modified conjugated diene-based polymer of the present invention described above. The composition of the present invention is characterized in that it comprises 0.1 to 200 parts by weight of the inorganic filler with respect to 100 parts by weight of the modified conjugated diene-based polymer of the present invention.

As said inorganic filler contained in the composition of this invention, carbon black, a silica, etc. can be used individually or in mixture of 2 or more types. In particular, when blending an inorganic filler having a large number of functional groups on the surface of the inorganic particles such as silica, the performance of the modified conjugated diene-based polymer of the present invention can be further improved. The inorganic filler preferably has a pH of 3 to 7 when dispersed in a 4% aqueous solution in order to efficiently induce hydrolysis of the ester group or phenylether group of the functional monomer. If the pH is less than 3, corrosion of the processing equipment may occur during the mixing of the inorganic filler and the conjugated diene-based polymer, and if the pH is greater than 7, the hydrolysis rate of the ester group or the phenylether group of the functional monomer may be slow. Can be.

The compositions of the present invention are typically suitable for use for tire materials, in particular for tire treads, and thus may further comprise, in usual amounts, conventional additives that can be formulated into the composition for tires.

The modified diene polymer of the present invention is excellent in affinity with polar inorganic additives such as silica, and the composition obtained by incorporating inorganic or metal oxide particles alone or in combination of two or more thereof by using the same is not only improved in physical properties but also tire materials. In particular, when applied to a tire tread, the balance between low hysteresis loss and wet skid property is excellent, and low fuel efficiency and braking property are improved, and storage stability is excellent.

The present invention may be modified in various ways and may have various embodiments, but the present invention is provided below in order to help the understanding of the present invention, but the following examples are only for illustrating the present invention and the scope of the present invention. Is not limited to the following examples.

EXAMPLE

Experiment method

1. Polymer microstructure analysis

The microstructure of the polymerized polymer was confirmed using Bruker's 400 MHz 1 H-NMR.

2. Molecular Weight Measurement

Molecular weight was measured by connecting two polystyrene 5 μm mixed-C columns of PLgel in series and using THF as a solvent together with a polystyrene reference sample (molecular weight 5000 g / mol) and a polymerized polymer. The detector used a refractive index detector (RI).

3. Hydrolysis rate measurement

The hydrolysis rate of the conjugated diene-based polymer in which 0.2 parts by weight of I-1076, an antioxidant, was introduced, 50 phr of silica having a pH of 5 when dispersed in a 4% aqueous solution was introduced, and Thermo Scientific's Haake Polylab OS Rheodrive (Bumbury Rotor, kneaded at 150 ° C. for 3 minutes, cooled, dissolved in tetrahydrofuran (THF), filtered through a filter, and the solvent was removed from the filtrate, and then measured by ¹ H-NMR. The ester group hydrolysis (conversion to carboxylic acid after hydrolysis) was confirmed through the peak area of hydrogen of carboxylic acid of ˜12.3 ppm, and the alkoxyphenyl group hydrolysis (conversion to phenol group after hydrolysis) of 7.9 ppm of phenol group It was confirmed through the peak area of hydrogen. The conversion ratio was calculated in consideration of the ratio of the input amount of butadiene and functional monomer and the relative area ratio with respect to the peak area of butadiene units (4.3-6.1 ppm) in ¹ H-NMR.

4. Denaturation rate measurement

Two columns filled with silica gel (Zorbax PSM) were connected in series and measured with a refractive index detector (RI) using THF as a solvent. The polystyrene reference sample (molecular weight 5000g / mol) was dissolved in a solvent with a polymer and then injected into the column to measure. The modification rate was calculated by the following formula.

% Denaturation = [1- (A2 × A3) / (A1 × A4)] × 100

A1: total peak area of the sample (excluding polystyrene reference sample peak area) when the area of all peaks obtained from the styrene gel column is 100;

A2: When the area of all the peaks obtained from the styrene gel column is 100, the peak area of the polystyrene reference sample,

A3: When the area of all peaks obtained by a silica gel column is 100, the sample peak area which is not adsorbed by a silica gel,

A4: Peak area of the polystyrene reference sample when the area of all peaks obtained in the silica gel column is 100.

5. Tensile Experiment

The vulcanized test piece was prepared by c-type dumbbell, and measured using a universal testing machine (LLOYD UTM) according to the ASTM 412 tensile test method.

6. Viscoelastic properties

The viscoelastic properties of the vulcanized test specimens, tanδ, were measured with a temperature sweep at 10 Hz and 0.1% strain using a DMTA instrument. A high tan δ value at 0 ° C. is excellent in wet skidability as a braking property, and a low tan δ value at 60 ° C. indicates low hysteresis and excellent fuel economy.

7. Inorganic particle dispersibility

The dispersibility of the modified conjugated diene-based polymer and the inorganic particles was confirmed by Payne effect using Alpha Technology's RPA2000 as a sample before blending with Hakke and before vulcanization. The Payne effect was expressed as a difference between 0.2% and 40% of deformation at 0.1Hz and 60 ° C. The smaller the value, the better the dispersibility of the inorganic particles.

8. Pattern viscosity

The pattern viscosity of the modified conjugated diene-based polymer itself was measured based on ML (1 + 4) at 100 ℃ using the Mooney viscometer of Alpha technology.

9. Cold flow

Storage stability analysis measured the amount of flow for 1 minute at a pressure of 3.5 psi through a 1/4 inch orifice at a temperature of 50 ° C. A polymer piece having a width of 3 cm / length 3 cm / height 3 cm was placed on a glass plate inclined at an angle of 30 ° at room temperature, and compared with a phenomenon in which the length of the specimen was increased by flow after one day.

Example 1

34g of styrene, 126g of 1,3-butadiene, and 830g of hexane were added to a 2L autoclave reactor, 0.9ml of tetramethylethylenediamine (TMEDA) was added thereto, and the reactor temperature was raised to 40 ° C. while being turned into a stirrer in a nitrogen atmosphere. When the reactor temperature reached the set temperature, 5.6 mL of 0.3 M butyl lithium (n-BuLi) was added to carry out the polymerization reaction. 10 minutes after the reaction temperature reached the maximum temperature, 80 mmol of t-butyl methacrylate was added to further polymerize and trimethylolpropane triglycidyl ether for coupling. 3 mmol was added, and after an additional 10 minutes, ethanol was added to stop the polymerization, and the polymer solution was discharged from the reactor, and the antioxidant Irganox-1076 was added to 0.2 parts by weight based on 100 parts by weight of the polymer. In order to remove hexane, which is a solvent of the polymer, the prepared polymer was placed in heated hot water, stirred to remove the solvent, and then roll dried to remove residual solvent.

Example 2

Except for using t-butyl acrylate (t-butyl acrylate) instead of t- butyl methacrylate, it was carried out in the same manner as in Example 1.

Example 3

Except for using trimethylsilyl methacrylate (trimethylsilyl methacrylate) instead of t- butyl methacrylate was carried out in the same manner as in Example 1.

Comparative Example 1

The same procedure as in Example 1 was carried out except that t-butyl methacrylate was not used.

Comparative Example 2

Except for using methyl methacrylate (methyl methacrylate) instead of t-butyl methacrylate was carried out in the same manner as in Example 1.

Experimental Example: Kneading of Polymers and Inorganic Materials and Measurement of Physical Properties

Each of the polymers obtained in the above Examples and Comparative Examples was combined with the composition shown in Table 1 to prepare a composition. The kneading method of the polymer composition was made using Thermo Scientific's Haake Polylab OS Rheodrive, and a Bumberry rotor was used.

Blending proceeded in two steps. Kneading is the first kneading, 75% by weight, polymer, filler (silica), oil, zinc oxide (ZnO), stearic acid, silane coupling agent (Si-69), 6 at a rotor speed of 60 rpm -PPD was added to control the temperature to obtain a primary composition at 160 ℃. In the second kneading, the compound obtained in the first kneading is cooled to room temperature, and sulfur, diphenyl guanidine (DPG: Diphenyl Guanidine) and N-cyclohexyl-2-benzothiazole sulfonamide are cooled to 100 ° C. or lower. (CBS: N-cyclohexyl-2-benzothiazole sulfonamide) was added and kneaded for 5 minutes. The blended composition was vulcanized at 170 ° C. in a T90 + 5 min press to produce vulcanized rubber specimens.

TABLE 1

Physical property analysis and performance of the polymer and polymer composition prepared according to the present invention were evaluated, and are shown in the following [Table 2] and [Table 3], respectively.

TABLE 2

* Styrene content and vinyl content are the result calculated by H-NMR.

* Vinyl content is the proportion of vinyl groups produced by 1,2-bonds in all butadiene monomers.

TABLE 3

As shown in Table 2 and Table 3, Examples 1 to 3 according to the present invention, the hydrolysis rate, denaturation compared to Comparative Examples 1 to 2 by converting the ester group of the functional monomer introduced into the polymer by the hydrolysis of the carboxylic acid group It has high dispersion rate, high tensile strength and 300% modulus, and shows excellent dispersibility when blended with filler.Because of high tanδ at 0 ° C when used as a tire tread, it has excellent braking property on wet roads and tanδ at 60 ° C. It showed the characteristics of modified diene rubber material with excellent fuel efficiency with low road resistance.

On the other hand, Comparative Example 1 is a case in which the functional monomer of the present invention is not used, the silica dispersibility is low, and as a result, the tensile strength and 300% modulus are very low compared to Examples 1 to 3, Comparative Example 2 In the case of using a methacrylate-based monomer similar to the functional monomer of the invention, since it is composed of a methyl ester group that is not hydrolyzed well, the polarity improvement is not achieved as in the case of introducing the functional monomer of the invention. Properties such as acidity, tensile strength, 300% modulus, etc. were inferior to Examples 1 to 3, but methyl methacrylate monomer was superior to Comparative Example 1 because of its higher polarity than SBR. Examples 1 to 3 and Comparative Example 2 confirmed that the storage stability (cold flow) is improved compared to Comparative Example 1.

Claims (10)

1. Modified conjugated diene-based polymer comprising a functional monomer represented by the following formula (1) at least one of the start end and end end of the polymer chain:

   [Formula 1]

   

   Here, R ₁ is hydrogen or an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ₂ is an alkyl group having 4 to 20 carbon atoms including a tertiary carbon, or an aryl group having 6 to 20 carbon atoms. Or an alkylsilyl group having 3 to 20 carbon atoms and 1 to 10 silicon atoms, or an arylsilyl group having 6 to 20 carbon atoms and 1 to 10 silicon atoms, and R ₂ is separated by a thermal or acid catalyst to obtain an ester of the monomer. The group is converted to a carboxylic acid group or an anhydride.
2. The method of claim 1, wherein the functional monomer is selected from tert-butyl acrylate, tert-butyl methacrylate, trimethylsilyl acrylate, trimethylsilyl methacrylate, triethylsilyl acrylate, and triethylsilyl methacrylate. Modified conjugated diene-based polymer, characterized in that one or two or more compounds selected.
3. The modified conjugated diene-based polymer according to claim 1, wherein the polymer contains 1 to 100 functional monomers.
4. The modified conjugated diene-based polymer according to claim 1, wherein the functional monomer is included in an oligomeric block structure in the polymer.
5. The polymer is prepared by (co) polymerizing at least one diene monomer or copolymerizing a diene monomer and a vinyl aromatic monomer, and adding the functional monomer to polymerize the polymer. Modified conjugated diene polymer.
6. The modified conjugated diene according to claim 5, wherein the diene monomer is at least one selected from 1,3-butadiene and isoprene, and the vinyl aromatic monomer is at least one selected from styrene and alpha methylstyrene. System polymers.
7. A composition comprising 0.1 to 200 parts by weight of the inorganic filler with respect to 100 parts by weight of the modified conjugated diene-based polymer according to any one of claims 1 to 6.
8. 8. The composition of claim 7, wherein the inorganic filler is a carbon black filler, a silica filler, or a mixture thereof.
9. 8. The composition of claim 7, wherein the inorganic filler has a pH of 3 to 7 when dispersed in a 4% aqueous solution.
10. The composition according to claim 7, wherein the composition is a composition for a tire material.