TW201041914A - Branched conjugated diene-aromatic vinyl copolymer and method for producing same - Google Patents

Abstract

A branched conjugated diene-aromatic vinyl copolymer (C) being a random copolymer, wherein the aromatic vinyl bond content in the conjugated diene-aromatic vinyl copolymer (C) is from 30 to 38 mass%, the vinyl bond content in the total bond units of the conjugated diene is from 30 to 43 mol%, the weight average molecular weight (Mw-C) in terms of polystyrene obtained by gel permeation chromatography (GPC) of the conjugated diene-aromatic vinyl copolymer (C) is from 700,000 to 1,000,000, the ratio of the weight average molecular weight (Mw-C) to the number average molecular weight (Mn-C) ((Mw-C)/(Mn-C)) is from 1.7 to 3.0, and the Mooney viscosity (ML-C) and the Mooney relaxation ratio (MSR-C) measured at 120 DEG C satisfy the relationship represented by formula (1): {214-(ML-C)}/300 = (MSR-C) = {260-(ML-C)}/300 (wherein 100 = (ML-C) = 140).

Description

201041914 VI. Description of the Invention: [Technical Field] The present invention relates to a branched conjugated diene-aromatic ethylene copolymer and a process for producing the same. [Prior Art] From the viewpoint of ensuring safety, it is important for automobile tires to use materials which are excellent in wet skid resistance and have practically sufficient wear resistance and destructive properties. On the other hand, in recent years, environmental considerations such as suppression of carbon dioxide emissions have become social requirements, and the demand for low fuel consumption of automobiles has also increased. In this regard, as a material for automobile tires, particularly tire surfaces in contact with the ground, it is required to develop a material having a small rolling resistance. Further, in view of the life cycle of the tire, the concern for the reduction of the energy consumption in the manufacturing step is also improved, and in particular, a rubber material having a low workability and a low processing energy when the compound is mixed is required. Further, it is required to have good productivity in the production of raw synthetic rubber and to reduce energy consumption. As one of the main materials of the tire tread, styrene-butadiene rubber (SBR) is known. As a polymerization method of SBR, there are an emulsion polymerization SBR (E-SBR) obtained by radically polymerizing a monomer suspended in water, and a solution polymerization obtained by anion polymerization of a monomer in a hydrocarbon solvent using an organic alkali metal. SBR (S-SBR). Among these, the solution polymerization SBR (S-) is excellent in the balance between the fuel consumption performance and the wet skid resistance in the tire having a high degree of freedom in polymer structure design, especially using ruthenium dioxide as a filler. The use of SBR) has increased. As a polymerization process of solution polymerization SBR (S-SBR), it is roughly divided into two types: batch processing 147412.doc 201041914 polymerization process and continuous polymerization process. Ο

In the batch polymerization process, a functional group can be introduced relatively easily by adding a modifier to the active terminal ' of the polymer, and a rubber having a small rolling resistance when the tire surface material is formed can be obtained (for example, Refer to Patent Document 1). On the other hand, since the molecular weight distribution is narrow, and the viscosity of the mixture is increased by the combination of the modified group and the filler such as cerium oxide, the viscosity is increased during the kneading, so that the processing property is poor, and the temperature rise and the cooling operation are required for each batch during the polymerization. Therefore, it also has the disadvantage of increasing energy consumption. On the other hand, in the continuous polymerization process, the heat generated by the exothermic reaction of the polymerization can also initiate the polymerization or promote the heating required, so the energy consumption per unit throughput is less than the batch polymerization process, and The molecular weight distribution is also wide, so it also has the advantage of better processability. However, solution-polymerized SBR (S-SBR) has a disadvantage of high energy consumption and poor processability when compounding a compound in the production of a composition, compared with an emulsion formed by a large amount of branches in the polymerization. . As another technique, for example, a method of coupling a co-consumed diene-aromatic ethylene copolymer obtained by anionic polymerization in a continuous polymerization process using a tri- or more functional tetracycline such as tetrachloropyr (for example) can be mentioned (for example, , refer to Patent 2); using halogen-containing Shishi compound, ρ5 1 mouthwash alkoxy decane compound, alkane gas sulfur test compound, etc.

A method of coupling a compound having two or more epoxy groups, such as a compound of J oxy group (for example, refer to Patent Document 4), etc. [Prior Art Document] [Patent Document] I47432.doc 201041914 [Patent Document 1 [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A-61-255917 [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. [Invention No. 01/23467] [Problems to be Solved by the Invention] However, the vulcanized rubber is excellent in workability, and the balance between low hysteresis loss and wet skid resistance in the case of producing a vulcanized rubber is excellent. The conjugated diene aromatic ethylene copolymer having practically sufficient abrasion resistance and destructive properties has room for improvement in production. Further, the techniques disclosed in Patent Documents 2 to 4 are necessary to obtain a high coupling ratio. The polymerization is carried out under conditions of relatively low temperature, so there is still room for improvement in productivity. The present invention has been developed in view of the above circumstances, and its object is to provide a branched conjugated diene_aromatic B. Copolymer, and a method for producing the same\The branched conjugated diene-aromatic ethylene copolymer has good processability in forming a vulcanized rubber temple, and has low hysteresis and resistance to slipping when it is made into vulcanized rubber. The balance of the properties is excellent, and the wear resistance and the damage characteristics are also sufficient in practical use, and the productivity is also excellent. [Technical means for solving the problem] The inventors of the present invention have conducted intensive studies to solve the above problems and found that The branched conjugated diene aromatic ethylene copolymer and the solution of the two V], the 3 cc branching total diene-aromatic ethylene copolymer of the square aromatic ethylene bond amount, the total conjugated diene The ethylene bond 147412.doc 201041914 in the bonding unit, the weight average molecular weight (Mw-C), and the weight average molecular weight (Mw_c) / number average molecular weight (Mn-C) are specific numerical ranges, and are in i2〇< The woody viscosity (ML-C) and the woody relaxation rate (MSR-C) of the measured t satisfy the specific relationship; thus, the present invention has been completed. That is, the present invention is as follows. [1] A branched form Yoke diene-aromatic ethylene copolymer (c), a random copolymer; the amount of aromatic ethylene linkage in the conjugated diene-aromatic ethylene copolymer (c) is 30 to 38 mass% / 〇, a total of "--sparse total bond early element The amount of ethylene bond in the middle is 3 〇~4 3 mol%, and the polyphenylene obtained by gel permeation chromatography (GPC) of the above-mentioned common dilute-square aromatic copolymer (C) The weight average molecular weight (Mw-C) in terms of ethylene is 700,000 to 1,000,000, and the ratio of the weight average molecular weight (Mw-C) to the number average molecular weight (Mn_c) ((Mw-C) / (Mn-C)) is 1.7~3.0, the Mn-viscosity (ML-C) and the Mooney relaxation rate (MSR_C) measured at 120 °C satisfy the relationship of the following formula (1), {214-(ML-C)}/300S (MSR -C)S {260-(ML-C)}/3〇〇...(1) (In the formula (1), 100S (ML-C) S140). [2] The branched conjugated diene-aromatic ethylene copolymer (c) according to [1], which uses a polyfunctional modifier having four or more functional groups to make a total consumption of 147,412.doc 201041914 When the olefin-aromatic ethylene copolymer (i) is coupled, the conjugated diene-aromatic ethylene copolymer (1) has a polystyrene-equivalent weight average molecular weight (Mw-I) of 500,000 to 700,000 at 120 ° C. The measured Mui viscosity (ML_I) and the Munni relaxation rate (MSR-I) satisfy the relationship of the following formula (2), {260-(ΜΙ^-Ι)}/300$(Μ8ΙΙ-Ι)${ 310-(ΜΙ^Ι)}/300~(2) (in the formula (2), 65$ (ML-I)S 100). [3] A branched conjugated diene-aromatic ethylene copolymer composition containing a branched conjugated diene-aromatic ethylene copolymer (c) such as [1] or [2] and an inorganic filler Agent. [4] A process for producing a branched conjugated diene-aromatic ethylene copolymer (c) which is a branched conjugated diene-aromatic ethylene copolymer of [1] or [2] (C) a manufacturing method comprising the steps of: continuously supplying a solution containing a conjugated diene compound, an aromatic vinyl compound, and an anionic polymerization initiator to a reactor and subjecting it to polymerization to obtain an active terminal a step of conjugated a solution of a diene-aromatic ethylene copolymer; coupling the above-mentioned co-diene-aromatic ethylene copolymer with a polyfunctional modifier having four or more functional groups capable of reacting with the above reactive terminal The steps. [5] A method for producing a branched conjugated diene-aromatic ethylene copolymer (c) which is a branched conjugated diene of [1] or [2] _ aromatic ethylene copolymer 147412.doc 201041914 The method for producing (c); comprising the steps of: continuously supplying a solution containing a conjugated diene compound, an aromatic vinyl compound, and an anionic polymerization initiator to a reactor equipped with a stirrer; a step of a polymerization reaction; a step of continuously obtaining a solution of a conjugated diene-aromatic acetylene copolymer having an active terminal from an outlet of the above reactor; using a functional group having 4 or more functional groups capable of reacting with the above-mentioned active terminal & modifier's step of coupling the above-mentioned co-different hydrocarbon. Aromatic ethylene copolymer; and in the above polymerization, the internal temperature of the reactor outlet is maintained at 95 to 11 (rc ' with an average residence time of 15 The polymerization reaction is continuously carried out in a minute or more and 35 minutes or less. [6] A method for producing a branched-type diolefin-based ethylene-based polymer according to (4) or [5] wherein a functional group of the above polyfunctional modifier is used Total mole The above polyfunctional modifier is used in such a manner that the number of moles of the above anionic polymerization initiator is gi to M times. [Effect of the Invention] (4) The present invention can provide an excellent processability when the vulcanized rubber is produced. The low hysteresis and wet skid resistance of the vulcanized rubber also satisfies the method for producing a branched conjugated diene which is practically sufficient in abrasion resistance, breakage, and productivity. In the following, the embodiment for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following embodiment is intended to explain the present invention. The invention is not limited to the form shown in the following paragraphs. The present invention can be suitably modified within the range of its main structure. [Branched co-light-dilute hydrocarbon-aromatic ethylene copolymer] This embodiment The branched conjugated diene-aromatic ethylene copolymer (4)) is a random copolymer, and the aromatic ethylene bond amount in the above conjugated diene-aromatic ethylene copolymer (c) is 30 to 38. Quality%, total vehicle two The amount of ethylene bond in the total hydrocarbon bonding unit is from 3 to 43 mol%, and the weight average molecular weight (Mw_c) of the conjugated diene-aromatic ethylene copolymer obtained by Gpc is 7〇〇,〇〇〇~1,000,000 > The ratio of the weight average molecular weight to the number average molecular weight ((Mw_c) / (Mn-C)) is 1.7 to 3.0, and the Mooney viscosity (ML-C) measured at 120 °C The relationship with the Mooney relaxation rate (msr_c) satisfies the following formula (1). {214-(ML-C)}/300S (MSR-C)S {260-(ML-C)}/3 00...(1) (in equation (1), l〇〇S(ML-C) S140) The branched conjugated diene-aromatic ethylene copolymer (c) of the present embodiment is a random copolymer. Here, the term "random copolymer" means that the chain length of the aromatic vinyl group is 30 or more, or less. Branched conjugated diene-aromatic ethyl condensate copolymer 147412.doc -10· 201041914 in the present embodiment, if it is a random copolymer of a common hydrocarbon compound and an aromatic ethylene compound, No limit. The compound described below can be suitably used as the conjugated diene compound and the aromatic vinyl compound. As the common dilute hydrocarbon-aromatic ethylene copolymer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-butadiene isoprene copolymer, More preferred is a styrene-butadiene copolymer. For example, in the case where the branched composite-muth-aromatic ethylene copolymer (c) is a butadiene-styrene copolymer, the method of Kolthoff (IM KOLTHOFF, et 1·, J· Polym) is utilized. Sci. 1,429 (1946) The method of decomposing a branched total diene-aromatic ethylene copolymer (C) and analyzing the amount of polystyrene insoluble in methanol' The total amount of the branched diolefin-aromatic ethylene copolymer (C) is preferably 5% by mass or less, more preferably 3% by mass or less. Further, if the branched conjugated diene_aromatic ethylene copolymer (C) is decomposed by the decomposition of ozone and the styrene chain distribution is analyzed by gel permeation chromatography (GPC), it is preferred. It is a single styrene (that is, a styrene unit chain of 1 styrene) is 40% by mass or more of the total bonded styrene, and more preferably a long-chain block styrene (that is, a styrene unit bond of 8 or more) The styrene) is 5% by mass or less of the total bonded styrene. The aromatic ethylene bond amount in the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment is from 30 to 38% by mass, preferably from 32 to 37% by mass. The amount of the aromatic vinyl bond can be determined by measuring the ultraviolet absorption of the phenyl group of the branched conjugated diene-aromatic ethylene copolymer (C). Further, the ethylene bond amount in the total bonding unit of the conjugated diene is 30 to 43 mol 1474 l2.doc -11 - 201041914 ear%, preferably 32 to 42 mol%. For example, in the case where the branched conjugated diene-aromatic ethylene copolymer (C) is a butadiene-styrene copolymer, it can be by the method of Hampton (RR Hampton, Analytical Chemistry 21, 923 (1949) The method disclosed in the method) is to determine the amount of ethylene bond (1, 2 bond amount) in the butadiene bonding unit. The conjugated diene-aromatic ethylene copolymer is generally mostly mixed with natural rubber or butadiene rubber to form a vulcanized rubber, and the respective bonds of the branched diolefin-aromatic ethylene copolymer (C) are branched. When it is within the above range, it is neither excessively compatible with the rubber nor excessively separated from the rubber, and can be mixed in a good balance. Thereby, a vulcanized rubber excellent in balance between low hysteresis loss resistance and wet skid resistance can be obtained. The glass transition temperature of the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment is preferably -40 to -15 ° C, more preferably -35 to -18 ° C. By the glass transition temperature in this range, a vulcanized rubber excellent in balance between low hysteresis loss resistance and wet skid resistance can be obtained. Regarding the glass transition temperature, according to IS022768: 2006, the DSC curve is recorded while raising temperature in a specific temperature range, and the peak of the DSC differential curve (Inflection point) is set as the glass transition temperature. The branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment has a weight average molecular weight (Mw-C) in terms of polystyrene as described above of 700,000 to 1,000,000, preferably 750,000 to 950,000. In order to obtain good wear resistance and strength, it is 700,000 or more, and it is set to 1,000 or less in order to maintain good workability. Further, the ratio of the weight average molecular weight (Mw-C) to the number average molecular weight (Mn-C) ((Mw-C) / (Mn-C)) is 147412.doc 201041914 1·7~3·〇, preferably It is 2·0~2.8. In order to obtain good workability, it is i 7 or more, and is 3.0 or less in order to obtain good mechanical properties. The molecular weight and molecular weight distributions were determined by GPC using a chromatogram and based on a calibration curve using standard polystyrene. The branched conjugated diene-aromatic ethylene copolymer (c) of the present embodiment has a Mooney viscosity (ML-C) and a Mooney relaxation rate (MSR c) measured at 120 ° C satisfying the following formula ( 1) The relationship. ◎ {214-(ML-C)}/300S(MSR-C)S {260-(ML-C)}/300...(1) (here, 100$(ML-C)S140) The rate (MSR) is the torque (Τ) and time (t) after the rotor is stopped by the method specified in IS0289-4: 2003, and the rotor is stopped after 6 seconds to 5 seconds. (seconds)) The absolute value of the slope when making a double logarithmic plot. In the case where the viscosity is equal, the more branches, the smaller the value, and thus can be used as an indicator of the degree of branching. Specifically, it can be obtained by the method disclosed in the examples described later. The Mooney viscosity and the Mooney relaxation rate are usually measured at 〇10 °C, but in the present embodiment, it is 12 Å. (: measured Moi viscosity and Mooney relaxation rate. When the formula (1) has a sufficient degree of branching in such a manner as to reach the above upper limit value, the workability is excellent, and the low hysteresis loss of the vulcanized rubber is &Excellent wet skid balance' is also full of practical wear resistance and damage characteristics. The higher the branching degree, the lower the MSR_C, the better the processability and the low hysteresis loss and wet skid resistance of vulcanized rubber. If the balance is excellent, if it is set to the lower limit or less, the coupling reaction must be increased, so that the productivity is lowered and it is not practical. 147412.doc -13· 201041914 This January is a conjugated diene_aromatic ethylene. The behavior of the copolymer was investigated and found to be a copolymer of the same microstructure (aromatic ethylene bonding amount and conjugated diene bond unit in the amount of female bond) and the same degree of branched state. , politics and "

The ML-C of the copolymer of molecular weight change is marked on the X-axis, and MSR_C is marked on the γ-axis. (msr_c/ml_c) can be approximated to a slope of -1/300. Furthermore, in the 颏 颏 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈 戈The distance has changed). From these findings, it was found that by satisfying the conditions of formula (1), the MSR-C and ML-C of the co-diene-smoke-aromatic ethylene copolymer (c) can provide a better branching state' and The ethylene bond amount, the weight average molecular weight (Mw_c), the ratio of the weight average molecular weight to the number average molecular weight ((Mw_c) / (Mn_c)) are controlled to a specific range, and the following polymer can be produced, and the polymer is produced. When the vulcanized rubber is cured, it has a good adhesion. When it is made into a vulcanized rubber, it has a good balance between low hysteresis loss and wet skid resistance, and is also practically sufficient for wear and damage characteristics. . Further, the relationship between ML-C and MSR-C is preferably such that the relationship of the following formula (la) is satisfied. The effect of the above-described embodiment can be made more remarkable by satisfying the relationship of the following formula (10). {220-(ML-C)}/300^(MSR-C)^ {255-(ML-C)}/300·.· (1 a) (here, 106g(ML-C)S135) Branched conjugated-ene-fe-aromatic ethylene copolymer (c) It is preferred to use a polyfunctional modifier having more than 4 pentylene groups to make the co-light dilute-aromatic ethylene Copolymer coupling. Thereby, it is effective to improve the branching degree and the molecular weight of 147412.doc -14· 201041914, and it is possible to obtain a copolymer which is excellent in workability in the production of a vulcanized rubber and excellent in the balance of properties of a vulcanized rubber. Further, the above conjugated diene-aromatic ethylene copolymer (c) is more preferably a polystyrene-equivalent weight average molecular weight (^1\^-1) of 500,000 to 700,000, and a Mooney viscosity measured at 120 °C. (ML-I) A conjugated diene-aromatic ethylene copolymer (J) which satisfies the relationship of the following formula (2) with a kiln relaxation rate (MSR_I). Thereby, a copolymer can be obtained which is excellent in workability when it is made into a vulcanized rubber, and is excellent in balance between low hysteresis loss and wet skid resistance when it is made into a vulcanized rubber, and is also sufficient for practical use. It has excellent wear resistance and destructive properties, and is also excellent in productivity. {260-(ML-I)}/3 00$ (MSR-I)g {310-(ML-I)}/3 00... (2) (here 'in equation (2), 65$ (ML-I)S100) Further, the Mooney viscosity (ml-I) measured at 120 ° C is better than the ii (the RMS measurement of the Mooney relaxation rate (MSR-I) is satisfied by the following formula (2) Hook relationship. {268-(ML-I)}/300^ (MSR-I)^ {3OO-(ML-I))/3 00-. (2a) (here 'in equation (2a), 66S (ML-I) S89) [Method for producing a knife-like total-smoke-aromatic ethylene copolymer] As the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment A preferred production method comprises the steps of: continuously supplying a solution containing a conjugated diene compound, an aromatic vinyl compound, and an anionic polymerization initiator to a reactor and subjecting it to a polymerization reaction to obtain an active terminal a step of a solution of a conjugated diene-aromatic ethylene copolymer; VIII 147412.doc • 15 - 201041914 using the polyfunctional modifier having four or more functional groups capable of reacting with the above reactive terminal to make the above conjugate a step of coupling a diene-aromatic ethylene copolymer. As a branch of the present embodiment A better manufacturing method of the conjugated diene-aromatic ethylene copolymer (C) includes the following steps: continuously supplying a conjugated diene compound, an aromatic vinyl compound, an anionic polymerization to a reactor equipped with a stirrer a step of conducting a solution of the initiator and subjecting it to a polymerization reaction; a step of continuously obtaining a solution of a total of a diene-di-aryl aromatic copolymer having an active terminal from the outlet of the reactor; and using the same activity as described above The step of coupling the polyfunctional modifier having four or more functional groups at the terminal reaction is carried out. According to the above production method, the processability in the case of producing a vulcanized rubber is good, and the hysteresis loss is high in the case of producing a vulcanized rubber. The branched total co-diene-aromatic ethylene copolymer (C) of the present embodiment which is excellent in balance between properties and wet skid resistance and which satisfies practically sufficient abrasion resistance and destructive properties. For example, previously When mixing a compound containing the above SBR, a closed mixer such as a Banbury mixer is used, and a small capacity used in a laboratory scale is used. For example, in the case of a mixer using a capacity of several liters or less, in the case of using a mixer which is used in a manufacturing step of a rubber product such as a tire (for example, a gluten is several hundred liters or more), kneading processing As a result, the problem of workability becomes more conspicuous. As a result, there is a tendency that the viscosity of the compound rises and the surface or edge of the texture of the compound is rough. The manufacturing method of the present embodiment is even such a scale 147412.doc •16· 201041914 When the case is enlarged, excellent workability can be maintained, so that the branched conjugated diene-aromatic ethylene copolymer (c) can be efficiently produced without ignoring the above problems. (Conjugated Diolefin Compound) The conjugated dilute hydrocarbon compound used for the production of the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment is not particularly limited, and examples thereof include 1 , 3-butadiene, isoprene, 2,3-dimercaptobutane, 1,3-pentadiene, 3-mercapto-1,3-pentadiene, 1> 3_g Diene, is·hexene-ene, and the like. These may be used alone or in combination of two or more. Among them, i, 3-butadiene and isoprene are preferred from the viewpoint of availability or economy. (Fangxiangzu vinyl compound) The aromatic vinyl compound used for the production of the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment may, for example, be stupid ethylene or p-methylstyrene. , α-methyl styrene, vinyl ethyl benzene, vinyl decyl xylene, vinyl naphthalene, stilbene, and the like. These may be used alone or in combination of two or more. Among these, styrene is preferred. In the total diene fe compound and the aromatic vinyl compound, the allenes and the B-type which may be contained as impurities may become an important factor for suppressing the polymerization I and the coupling reaction. Therefore, it is preferred to The concentration in the total monomer is less than 200 ppm. (Polymerization solvent) In the present embodiment, "a total of a diene compound and an aromatic ethylenic compound are usually copolymerized in a solvent. The solvent is not particularly limited, and examples 1474I2.doc • 17- 201041914 A hydrocarbon-based solvent such as a saturated hydrocarbon or an aromatic tobacco can be used. Specific examples thereof include linear and branched aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; cyclopentane 'cyclohexane; An alicyclic cigarette such as cyclohexane; a stupid, toluene, dimethyl benzoate t4 aromatic hydrocarbon and a hydrocarbon containing the mixture. (Monomer concentration) In the present embodiment, the monomer concentration of the total diuretic compound and the aromatic vinyl compound in the polymerization solution to be subjected to the polymerization reaction is not particularly limited, and from the viewpoint of productivity, it is preferred. The amount of 5 to 5 Qf is more preferably 10 to 30% by mass. (Anionic polymerization initiator) The anion polymerization initiator which can be used in the polymerization reaction of the present embodiment is not particularly limited, and for example, an alkali metal initiator or an alkaline earth metal initiator can be used. As the metal-based initiator or the soil-based metal-based initiator, all of the metal-based initiators or the soil-based metal initiators having the ability to initiate polymerization can be used. Among these, a compound containing at least one of an organic metal test compound and an organic alkaline earth metal compound is preferred. The organic metal compound is not particularly limited, and is considered to be reactive. The organic clock compound is preferably used as an organic clock compound, and examples thereof include a low molecular weight compound, an organic compound of a solubilized polymer, a compound containing lithium alone in one molecule, and a lithium having a plurality of molecules in the molecule. The compound, the bonding method of the organic group, the compound having a carbon clock bond, the compound having a nitrogen-to-clock bond, and the compound having a tin-chain bond, 1474l2.doc -18·201041914, and the like. Specifically, §: As the organic single-ring compound, a n-butyl group, a second H, a third H-positive group, a f-base clock, a stupid base, and a kiln can be cited. As the polyfunctional organic clock compound, a reaction of 2's butane, a second butyl group and diisopropyl benzene, 1,3,5-trisylbenzene, n-butyllithium and 1,3 can be cited. - a reaction of butadiene and divinylbenzene, a reaction of a n-butyl clock with a polyethylidene compound, and the like. 〇 exemplified by lithium dimethyl guanamine, bis-n-hexyl amide amine, and diisopropyl. It is a compound with a nitrogen-lithium bond, ethyl amide, a propylamine amine, lithium amide, lithium hexamethylene sulfoxide, and kienimine. Bell, Lan Lin, etc. Further, the organic alkali metal compound disclosed in the specification of U.S. Patent No. 5,708,092, the specification of U.S. Patent No. 2,241,239, and the specification of U.S. Patent No. 5,527,753, and the like. Particularly preferred are n-butyl lithium and second butyl lithium. These organolithium compounds may be used singly or in combination of two or more kinds thereof. Examples of the other organic alkali metal compound include an organic sodium compound, an organic potassium compound, an organic pure compound, and an organic planing compound (IV). Specific examples thereof include naphthyl sodium and naphthyl potassium, and lithium, sodium or potassium alkoxides, sulfonates, carbonates, decylamines and the like can be used. The organic alkali metal compound can also be used in combination with other organometallic compounds. The alkaline earth metal compound is not particularly limited, and examples thereof include an organomagnesium compound, an organic calcium compound, and an organic ruthenium compound. Specifically, 147412.doc -19·201041914 Further, 'dibutylmagnesium and ethylidene are exemplified. Magnesium, propyl butyl magnesium, and the like. It is also possible to use a compound such as a burnt alkoxide, a caustic acid salt, a carbonate or a guanamine. These organic alkaline earth metal compounds may be used in combination with an organic metal compound such as the above organic alkali metal-based initiator. (Polar compound) In the method for producing the branched conjugated diene-aromatic ethylene (c) of the present embodiment, the purpose of randomly copolymerizing the aromatic vinyl compound and the conjugated diene compound is as follows. Or for the purpose of controlling the microstructure of the copolymer of the dihalide portion of the copolymer, or for improving the polymerization rate, it is preferred to add a small amount of a polar compound such as a Lewis base. The polar compound is not particularly limited, and examples thereof include tetrahydrofuran, diethyl ether, diethylene glycol, ethylene glycol dibutyl bond, ethylene glycol dibutyl bond, diethylene glycol diammine, and diethylene glycol dibutylate. Ethers such as dimethoxybenzene, 2,2_bis(2·tetrahydrobial south base), and the like; tetramethylethylenediamine, diphenyl bond dicarboxylic acid: dimethylamine, triethylamine, a tertiary amine compound such as pyridine "quinidine"; an alkali metal alkoxide compound such as a second acetonitrile, a third butyric acid clock, a dibutyric acid, a sodium butyrate or a sodium pentanate; a metal salt of an organic acid such as a decanoyl benzoate; a triphenylphosphine (tetra) compound (4). The polar compound may be used singly or in combination of two or more. The amount of the polar compound used is in accordance with Pei I, the choice of the privateness of the effect, and ... especially limited, usually compared to the anionic polymerization to test the soil metal atoms! Moer is 〇·〇1~1〇〇莫耳. The metal or the above-mentioned polar compound is used as a polymer agent, and the adjustment key of the micro-L structure of W field can be used according to the amount of the desired vinyl bond. It is suitable for use. Thereby, it is possible to control the ethylene bond amount in the total bonding unit of the decadiene cigarette, and the majority of the polar compound in the copolymerization of the co-density*diene compound and the aromatic vinyl compound also has a total of 147412.doc -20·201041914 The effective randomization effect can be adjusted by adjusting the distribution of the aromatic vinyl compound in the copolymer or the block amount of the aromatic vinyl compound (for example, the amount of the styrene block) by using a polar compound. (aggregation step) Ο

The polymerization reaction of the conjugated diene compound and the aromatic vinyl compound can continuously supply the above-mentioned common diene compound, aromatic vinyl compound, anionic polymerization initiator, polymerization solvent, and, if necessary, a small amount of a polar compound to a specific mixer. The reactor is carried out by continuously flowing a solution of the conjugated diene-aromatic ethylene copolymer from the outlet of the reactor. Further, the monomer and/or the polymerization solvent may be brought into contact with the organometallic compound at a stage before being supplied to the reactor by a method disclosed in Japanese Laid-Open Patent Publication No. 2002-284814, which is caused by a trace amount of impurities. Polymerization inhibition is deactivated. The supply position of the monomer solution or the like and the outflow position of the copolymer solution are not particularly limited, and may be any of the bottom, the top, and any position between the reactors: position 'but preferably from the position near the bottom The body solution, the copolymer solution flows out from the position near the top. Generally, the conjugated olefin compound is preferentially polymerized in the anionic copolymerization D than the aromatic vinyl compound. Therefore, a part of the conjugated diene compound may be supplied from the upper portion of the reactor for the purpose of randomization. The polymerization reaction is preferably carried out by keeping the internal temperature of the outlet of the reactor at 95 to 11 〇 ° C, and performing the average retention time of the vehicle p-bend and the sputum retention time of 15 minutes or more and 35 minutes or less. 147412.doc •21 - 201041914 Here, the internal temperature of the reactor outlet refers to the temperature of the copolymer solution at the outlet of the reactor. In order to increase the reaction rate, improve productivity, and promote the thermal branching reaction caused by metallization, and form a moderate branching structure at the stage before the coupling reaction, it is preferred to set the internal temperature of the reactor outlet to 95 〇. Above C. On the other hand, in order to prevent deactivation by excessive metallization reaction or the like and to suppress the coupling reaction, it is preferred to set the following. The temperature of the copolymer solution can be adjusted by heat exchange by an external heat exchanger, an internal heat exchanger, or the like, or by controlling the temperature of the supplied monomer solution or the like. Further, it is preferred that the temperature of the copolymer solution in the lower portion of the reactor is 3 to 15 ° C lower than the internal temperature of the outlet of the reactor. Here, the internal temperature of the lower portion of the reactor means, in particular, the temperature measured by a thermometer provided at a position where the liquid is impregnated when the reactor is filled with one third of the total capacity. The position 'and is not directly affected by the flow of the monomer solution supplied to the reactor. In the case where the reactor is in a state of complete mixing, the internal temperature of the lower portion of the reactor is actually the same temperature as the internal temperature of the outlet of the reactor. Conversely, in the case of a plug flow state, a greater temperature difference between the inner temperature of the lower portion of the reactor and the inner temperature of the outlet of the reactor. Two: From, J; Yi; 5 hire 51 Ding ar #帝] Good: mix 'like' The inner temperature difference between the inner temperature and the outlet of the reactor is 3~15. The difference between the methods in the range of (: is in the range of D I σ can produce a moderate retention of the bucket, so that the thermal branching reaction of the copolymer proceeds moderately. The residence time is longer, and the conversion heat of the monomer above is obtained. From the point of view of the branching reaction, the viewpoint of the (4) or the effect of inhibition of the inactivation on the coupling reaction is 147,412.doc •22· 201041914. The viewpoint is preferably 35 minutes or less. The rate is preferably 95% or more, and more preferably 98% or more, more preferably 99% or more. The higher the conversion rate, the better the production cost per unit of product, and the smaller the load on the solvent recovery step, The productivity is excellent. Here, the conversion rate can be obtained by the method disclosed in the examples described later. The co-diene-aromatic ethylene copolymer (I) obtained in the polymerization step of the previous stage before the coupling step is used. The weight average molecular weight (Mw-I) of the polystyrene-converted Ο ^ obtained by GPC is not particularly limited, and is preferably from 50,000,000 to 700,000. From the viewpoint of obtaining good abrasion resistance and strength, it is preferred that 500,000 to From the viewpoint of productivity and the processability of the conjugated diene-aromatic ethylene copolymer of the present embodiment obtained after coupling, it is preferably 700,000 or less. Further, polymerization at a stage before the coupling step The ruthenium diene-aromatic ethylene copolymer (I) obtained in the step has a woody viscosity (ML-q I) and a woody relaxation rate (MSR-I) which are preferably measured at 120 ° C. Relationship of the following formula (2): {260-(ML-I)}/3 00^ (MSR-I)^ {3 10-(ML-I)}/3 00··* (2) (here , 65$ (ML-I)S 100) . In order to obtain a branching total diene-aromatic ethylene copolymer (C) obtained after coupling, having sufficient branching degree, in the above formula (2), In the coupling reaction carried out after the polymerization reaction, it is preferred to carry out the polymerization reaction so as to ensure a sufficient active terminal, preferably to a lower limit or more. The solution of 146412.doc -23- 201041914 which consumes the active end from the outlet of the reactor and consumes the dilute hydrocarbon. The aromatic (tetra) ethylenic copolymer has more than 4 kinds of reactions capable of reacting with the active end: The branched conjugated diene-aromatic ethylene copolymer of the present embodiment can be obtained by contacting the energy-based polyfunctional modifier with a coupling reaction. The reactor can be the same tank type with a mixer as the polymerizer. The reactor may be a tank type reactor with a blender or a static mixer than a polymerizer. It is preferred to sufficiently mix the solution of the conjugated diene-aromatic ethylene copolymer with a large amount. The functional modifier obtains a sufficient residence time in the reaction. From this point of view, in the case of using a tank type reactor equipped with a stirrer, the volume of the reactor is preferably a turbulent flow condition of the polymerizer. /20~1/5 volume. The residence time is not particularly limited, and from the above viewpoint, it is preferably from 1 minute to 1 hour, more preferably from 1 minute to 15 minutes. The reaction temperature of the coupling reaction is particularly limited. From the viewpoint of obtaining sufficient modification efficiency, it is preferably 50 to 11 ° C ', more preferably 70 to 11 Å. Hey. (Polyfunctional modifier having four or more functional groups) As the active end reaction which can be reacted with the active terminal of a fluorene-aromatic ethylene copolymer having an active terminal, which is used in the present embodiment, The polyfunctional modifier of the functional group is not particularly limited, and examples thereof include those selected from the group consisting of epoxy groups, several groups, tickate groups, acid amide groups, acid groups, acid ester groups, and tartaric acid. Ester group, episulfide group, thiocarbonyl group, sulfur carboxylate group, dithiocarboxylate group, sulfonium carboxylic acid oxime group, imine group, ethylidene group, dentate group, alkoxyalkyl group a compound of the group of 147412.doc -24- 201041914, one of a group consisting of an isocyanate group, a thioisocyanate group, a common group, a hetero-based group, and a vinyl group. Further, in calculating the molar number of the functional group, in view of the reactivity with the active terminal of the conjugated diene-aromatic ethylene copolymer having an active terminal, the epoxy group, the carbonyl group, the epoxide group, and the thiocarbonyl group are used. An alkoxy group of an imino group, an ethylenimine group, an exo-ilylene group, a conjugated diolefin group, an arylvinyl group, or an alkoxy fluorenyl group, as a monofunctional 't-ester group a carboxylic acid amide group, an acid anhydride group, a thiocarboxylate group, a dithiocarboxylate group, a thiol amide amide group, an isocyanate group, a thioisocyanate group as a bifunctional group, a phosphate group, a bismuth phosphate group Calculated as a trifunctional. The sum of the functional numbers of the above functional groups in one molecule of the polyfunctional modifier used in the present embodiment is 4

Examples of the polyfunctional modifier having an epoxy group include polyepoxy compounds such as polyepoxidized liquid polybutadiene; tetraglycidyl m-diphenyleneamine tetraglycidylaminodiphenyl. a glycidylamino compound such as decane, tetraglycidyl-p-phenylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane; 3-glycidoxypropyltrimethoxydecane , 3_glycidoxypropyl triethoxy decane, 3_glycidoxypropyl tributoxide, epoxidized soybean oil, epoxidized linseed oil, etc. having epoxy groups and other functional groups Compound. Further, examples of the polyfunctional modifier having an oxo group include tetramethoxy zeshi, (5) ethoxy consumption, tetrabutoxy ketone, and bis(triethoxy oxonyl) f-fired double. (Dimethoxy oxanthene) Ethylene, bismuth (bismethoxy fluorenyl) hexanyl (diethoxy fluorenyl) octyl, bis(triethoxyphosphoryl) ethylene , bis(trimethoxydecylmethyl)ethylene, M_double earth (three 147412.doc •25-201041914 ethoxy decyl)benzene, bis(3-trimethoxydecylpropyl)-N-indole Alkoxydecane compound such as amine; N-(l,3-dimercaptobutylene)-3-(triethoxydecyl)-1-propylamine, N-(l,3-dimethylbutylene ) 3-((tributoxyalkyl)-1-propylamine, N-(l-decylpropylene)-3-(triethoxysulfonyl)-1-propylamine, N-ethylene-3 a compound having an imido group and an alkoxyalkyl group, such as (triethoxydecylalkyl)_ι-propylamine or n-(3-triethoxyindolyl)-4,5-dihydroimidazole. Further, 'as a polyfunctional modifier having a halogen group, examples thereof include ruthenium tetrahydride, ruthenium tetrabromide, ruthenium tetraiodide, bis(trichlorodecanealkyl)ethane, 2,2,4,4,6, Halogenated decane compounds such as 6-hexa-2,4,6-triheptane, ^,^...hexamethyl dimethyl sulfonyl)ethyl]benzene; mono-trimethoxy decane, monobromotrimethyl An alkoxyhalogenated decane compound such as oxydecane, dimethoxydimethoxydecane, dibromodimethoxydecane, dimethoxymethoxydecane or tribromodecyloxydecane. Further, the jin may include a tin halide compound such as tin tetrachloride, tin tetrabromide or ditrichlorostannyl group; and a polydentate phosphorous compound such as 1 chlorophosphine or tribromophosphine. A lot better - & this team 丨王 w. q door lift: a compound with a 矽, a more affinity functional group, a coupling molecule, a 4~6 functional polyepoxide ring A compound of an oxy group and an alkoxy group (IV). Examples of the hexafunctional modifier include hydrido glycerylation in which an amine is contained in the molecule, and more preferably, an amine group is contained. Further, a compound having an i molecule can be mentioned. You 丨, refractory glycerylamine; 'Can be cited tetraglycidyl dimethyl phenyl I47412.doc -26- 201041914 glycidylamino diphenyl carbaryl, tetraglycidyl · p-phenylenediamine tetraglycidyl Base-1,3-diaminomethylcyclohexane or the like. It is also possible to use two or more types. The total number of moles relative to the anionic polymerization initiator functional group is preferably such that the above polyfunctional modifier can be added alone to the amount of the polyfunctional modifier, the molar number, and the polyfunctional modifier.定U.1〜借士--··σ 巧 飔 飔 飔 而 而 而 而 而 而 而 而 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧 巧

Adding 0.1 times or more '+ from the viewpoint of economy, such as rainbow with β 恍 and 3, preferably 0.5 times or less. As described above, the coupling reaction is carried out by bringing a solution of a conjugated diene-aromatic ethylene copolymer having an active terminal into contact with a polyfunctional modifier having four or more functional groups capable of reacting with an active terminal. The branched conjugated diene-aromatic ethylene copolymer (c) of the present embodiment is obtained. As described above, after the coupling reaction, a specific deactivator, neutralizer or the like may be added to the solution as needed. Examples of the deactivator include alcohols such as water, methanol, ethanol, and isopropyl alcohol. Examples of the neutralizing agent include carboxylic acids such as stearic acid, oleic acid and tert-carbonic acid, aqueous solutions of inorganic acids, and carbonic acid gas. Further, since the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment also has its own yttrium viscosity, the viewpoint of preventing gelation in the finishing step after polymerization is considered. Or, in view of improving stability during processing, it is preferred to add 2,6-di-t-butyl-4-yl-perylene (BHT) or n-octadecyl-3-(4) as needed. '-Hydroxy-3,5,2-di-t-butylphenol) propionate, 2_mercapto-4,6-bis[(octylthio)methyl]phenol, etc., known rubber 147412.doc - 27- 201041914 Stabilizer for glue. From the viewpoint of further improving the processability of the branched conjugated diene-aromatic acetonitrile copolymer (c) of the present embodiment, it is preferred to add an extender oil. The method of addition is not particularly limited, and it is preferred to add and mix the extender oil to the polymer solution, and to carry out the desolvent for the oil-storage copolymer solution. The extender oil is not particularly limited. For example, an aromatic oil, a naphthenic oil, a paraffin oil or the like can be used, and an aromatic oil substitute having a polycyclic aromatic component of 3% by mass or less according to the IP346 method is preferred. Among these, an aromatic oil having a polycyclic aromatic component of 3% by mass or less is used as a substitute, but from the viewpoints of environmental safety, oil spill prevention, and wet grip performance, etc. Examples of the preferred aromatic oil substitutes include TDAE (Treated Distillate Aromatic Extracts), MES (Mild Extraction Solvate), and the like, and RAE (Residual Aromatic Extracts) as shown by Kautschuk Gummi Kunststoffe 52 (12) 799 (1999). The amount of the extender oil to be used is not particularly limited, and is usually 10 to 60 parts by mass, preferably 10 to 60 parts by mass, based on the branched conjugated hydrocarbon-aromatic ethylene copolymer (C) of the present embodiment. More preferably, it is 20 to 37.5 parts by mass. The method of obtaining the branched conjugated diene-aromatic ethylene copolymer (C) of the present embodiment from the polymerization solution is not particularly limited, and a conventionally known method can be applied. For example, it can be applied to a method in which a solvent is separated by steam stripping, a polymer is separated by filtration, and then dehydrated and dried to obtain a polymer; it is concentrated in a rinse tank, and further removed by a vented extruder or the like. Volatile method; direct devolatilization using a barrel dryer or the like 147412.doc -28- 201041914 method of sending points, and the like. [Branched total diene-alcohol-aromatic ethylene copolymer composition]

G

The branched conjugated diene-aromatic ethylene copolymer composition refers to a branched co-planar dilute tobacco-aromatic copolymer (c) t mixed with a specific material in the above embodiment. Adult. Examples of the material include a rubbery polymer other than a branched bipotarohydrocarbon-aromatic ethylene copolymer, an inorganic filler, an anthracycline coupling agent, a rubber softener, a vulcanizing agent, and an accelerated vulcanization. Agents • Vulcanization aids, etc. Such towels are preferably those which contain at least an inorganic filler. Preferably, gp is a branched conjugated diene-aromatic ethylene copolymer composition comprising the branched total diene aromatic ethylene copolymer (c) of the present embodiment and an inorganic filler. Examples of the rubbery polymer other than the scalloped total diene/aromatic ethylene copolymer (6) include a conjugated diene polymer or a hydride conjugated quinone diene compound and a vinyl group. a random compound of an aromatic compound, a polymer or a hydride thereof, a copolymer of a conjugated diene compound and a vinyl aromatic compound or a hydrogenated product thereof; a non-dihydrocarbon polymer, a natural rubber or the like. Illustrated. Butadiene rubber or its hydride, isoprene rubber or its hydride, I ethylene - butadiene rubber or its hydride, styrene butadiene - dilute block copolymer or its hydride a styrene-isopentadiene block ruthenium polymer or a styrene-based elastomer such as a styrene-based elastomer acrylonitrile butadiene rubber or a hydride thereof. Further, examples of the non-diuretic polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diuretic rubber, and I47412.doc •29·201041914 olefin- Olefin elastomer such as butene rubber, ethylene-hexene rubber, ethylene-octene rubber, butyl rubber, bromobutyl rubber, acrylic rubber, fluororubber, polyoxyethylene rubber, chlorinated polyethylene rubber, surface chlorine Alcohol rubber, αβ_unsaturated nitrile-acrylate-conjugated diene copolymerized rubber, urethane rubber, polysulfide rubber, and the like. The rubbery polymer may be a modified rubbery polymer having a functional group. The molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 1, 5 GG, GGG. A low molecular weight so-called liquid rubber can also be used. These rubbery polymers may be used singly or in combination of two or more. In the case where the rubbery polymer is combined in the branched conjugated diene-aromatic ethylene copolymer (c) of the present invention, the ratio is not particularly limited, and low hysteresis loss is obtained. It is excellent in the balance of wet skid resistance and also satisfies the vulcanized rubber which is practically sufficient in abrasion resistance and destructive properties. 5 As a branched conjugated diene_aromatic ethylene copolymer (c) / the above rubbery polymerization Preferably, it is 20/804 〇〇/〇, more preferably 30/70 to 90/10' and further preferably 50/50 to 80/20. 〇 The inorganic filler may, for example, be a cerium oxide-based inorganic filler or carbon black. Examples of the cerium oxide-based inorganic filler include solid particles in which SiO 2 or Sl 3 Al is a main component of a structural unit. Here, the main component and the knives refer to a cerium oxide-based inorganic filler which is cerium oxide-based inorganic filler, and examples thereof include cerium oxide, clay, and talc. , mica 'Shiyoshizao soil, ash stone montmorillonite, boiling 147412.doc • 30· 201041914 Stone, glass fiber and other inorganic fibrous substances. Further, a mixture of a surface-oxidized dioxo-based inorganic filler or a ceria-based inorganic filler and an inorganic filler other than the emulsified (four) may be used. Among these, sulfur dioxide and glass fiber are preferred, and silica dioxide is more preferred. As the dioxotomy, dry dioxotomy, wet dioxotomy, synthetic oxalate, or the like can be used. Among these, wet cerium oxide which is excellent in both the effect of improving the damage characteristics and the wet skid resistance is preferable. Ο ❹ = dendritic co-diene diene-aromatic ethylene polymer composition, obtained from the viewpoint of good wear resistance and destruction characteristics, the above-mentioned dioxic inorganic filler The nitrogen adsorption specific surface area obtained by the bribe adsorption method is preferably 100 to 300 m 2 /g, more preferably _0 m /g. In addition, it is also possible to use a dioxent inorganic filler having a relatively small specific surface area (for example, a specific surface area not exceeding the fan m2/g) and a relatively large specific surface area (for example, 200 ni 2 /g or more - for preparation) One of the m/g or more emulsified lanthanide inorganic fillers is used in combination, and the good abrasion resistance or fracture characteristics are highly balanced with low hysteresis loss. The amount of the cerium oxide-based inorganic filler in the branched conjugated diene-aromatic ethylene copolymer composition is not particularly limited, and is equivalent to the branched-type co-consumption dimethanol-aromatic ethylene copolymer. The rubber component (10) parts by mass of (c) is preferably from 0.5 to 300 parts by mass, more preferably from 5 to 2 parts by mass, even more preferably from 2 to 1 part by mass. In view of the effect of addition as a filler, it is preferred to add 〇'5 parts by mass or more, and on the other hand, the inorganic filler is sufficiently dispersed to add 147412.doc 31 201041914 The viewpoint of the physical or mechanical strength is preferably 300 parts by mass or less from the viewpoint of being practically sufficient. Carbon black is not particularly limited, and SRF (Semi-Reinforcing Furnace, semi-reinforcing carbon black), FEF (Fast Extruding Furnace), HAF (High Abrasion Furnace), ISAF can be used. (Intermediate Super Abrasion Furnace, Super Abrasion Furnace, SAF (Super Abrasion Furnace), various types of carbon black, preferably nitrogen adsorption specific surface area of 50 m2 / g or more, DBP ( Dibutyl phthalate, dibutyl phthalate) A carbon black with an oil absorption of 80 mL/100 g or more. The blending amount of the carbon black is preferably from 0.5 to 100 parts by mass, more preferably from 3 to 100% by mass, per 100 parts by mass of the rubber component containing the branched conjugated diene-aromatic ethylene copolymer (C). Further, it is preferably 5 to 50 parts by mass. From the viewpoint of exhibiting performance required for applications such as dry grip performance and electric conductivity, it is preferred to add 0.5 parts by mass or more, and from the viewpoint of dispersibility, it is preferably set to 100 parts by mass. the following. Further, in the branched conjugated diene-aromatic ethylene copolymer composition, a metal oxide or a metal hydroxide may be added in addition to the above-mentioned ceria-based inorganic filler or carbon black. Here, the term "metal oxide" refers to a solid particle having a chemical formula of MxOy (where M represents a metal atom and X and y represent an integer of 1 to 6, respectively) as a main component of a structural unit, and examples thereof include alumina, titania, and oxidation. Magnesium, oxidation, etc. Further, a mixture containing a metal oxide and an inorganic filler other than the metal oxide may also be used. The metal hydroxide is not particularly limited, and examples thereof include hydrazine hydroxide, hydrogen peroxide 147412.doc-32-201041914 magnesium oxide, and hydrazine hydroxide.

A dream-like coupling agent may also be added to the scalloped light-dilute-aromatic ethylene copolymer composition. The decane coupling agent has a function of causing the rubber component to act in close phase with the oxidized cerium inorganic i-filling agent, and has a basis for affinity or binding of the rubber-forming knives and the cerium oxide-based inorganic fillers, respectively. The slave system uses a sulfur-bonded moiety in one molecule with an alkoxyalkyl group, an oxy group. The compound of the sickle. From the above viewpoints, a preferred cerium of the sulphur coupling agent is used in combination with the above-mentioned cerium oxide-based inorganic filler. Specific examples of the decane coupling agent include bis-[3·(triethoxydecyl)-propyl-1·tetrasulfide, and double ♦ (triethoxy oxo) gastric propyl]-disulfide. , bis-[2-(triethoxyshixixian)_ethyl]_tetrasulfide, and the like. The blending amount of the Shi Xiyuan coupling agent is preferably 0.H0 parts by mass, more preferably G5 2 parts by mass, and further preferably 1 part by mass, based on the above-mentioned dioxic inorganic filler. . From the viewpoint of blending the yarn, the difficulty of the Shi Xiyuan coupling agent is preferably more than the Qlf amount, and it is preferably 3 parts by mass or less from the viewpoint of economy. In order to improve the workability, a softener for rubber may be blended in the branched conjugated diene-aromatic ethylene copolymer composition. Examples of the rubber softener include mineral oil or a liquid or low molecular weight synthetic softener. A mineral oil-based rubber softener used as a processing oil or a dilute oil for the softening, compatibilizing and enhancing of rubber is a mixture of an aromatic ring, a naphthenic ring and a paraffin chain, and a paraffin chain. The carbon number accounts for %% of the total carbon. The above is called the rocky system, and the carbon number of the ring-burning ring is 3Q~45%. Material and Branching 147412.doc •33- 201041914 The conjugated olefin aryl g-ethane oxime copolymer (c) is a rubber softener used together. It is preferred because it has a good suitability for aromatic compounds. The amount of the rubber softener to be added is 100 parts by mass, preferably 0 to 100 parts by mass, based on the rubber containing the branched total diene-square aromatic ethylene #polymer (C). 1 to 9 parts by mass, and more preferably 30 to 90 parts by mass. The amount of the softener for rubber is more likely to cause bleed out than the amount of the above-mentioned rubber component of 100 parts by mass, more than (10)f, which is present on the surface of the composition. It is not good for the adhesion, and it is not good. For the mixing of branched and branched diaromatic aromatic ethylene copolymer (6) and other rubbery poly 4, cerium oxide inorganic filler, carbon black or other filler, A method of various additives such as a material coupling agent and a softener for rubber is not particularly limited. For example, 'opening roller, Bamburi mixer, kneader, single screw extruder, double screw extruder, Multi-screw extruder, etc. Method; a method of dissolving and mixing the components, heating and removing the solvent, etc. Among these, in terms of productivity and good mixing, it is preferable to use a roller, a Bambu mixer, a pinch-type machine- Or extrusion; ^ and other melt tear practice. - Sub-mixed light diene aromatic ethylene copolymer and a variety of prescriptions of the square &, the method of mixing several times. The above-mentioned branched co-conducting dihydrocarbene-aromatic ethyl bromide copolymer composition may also be a vulcanization composition which is subjected to a vulcanization treatment by a ferulic agent. The vulcanizing agent is not particularly limited, for example, an organic peroxide may be used. And a radical generating agent such as an azo compound, an anthracene compound, a nitroso compound, a polyamine compound, or a guillotine. As the sulfur compound, for example, sulfur monochloride, 147412.doc-34-201041914 gas can be cited. Sulfur, a disulfide compound, a polymer polysulfide compound, etc. The amount of the vulcanizing agent used is not particularly limited, and is usually 1 part with respect to the rubber component containing the branched conjugated diene-aromatic ethylene copolymer (c). 〇 mass part, preferably 0.01~2 0 parts by mass, more preferably 1 to 15 parts by mass. The vulcanization method is not particularly limited, and a conventionally known method can be applied. The vulcanization temperature is, for example, 120 to 200 ° C, preferably 140 to 18 (TC. vulcanization). When necessary, vulcanization accelerators or vulcanization aids may be used as needed.

Particularly limited, previously known materials can also be used. For example, a vulcanization accelerator such as a sulfinamide, an anthraquinone, a thiuram, a acenaphine, an acid-ammonia, a (iv), a thiourea or a dithiocarbamate may be mentioned. Vulcanization aids and helmets are specially limited to 'can also be known as materials. For example, white, stearic acid, etc. are mentioned. The amount of the vulcanization accelerator used is usually 1 part by mass based on the rubber component containing the branched biphenylene-aromatic ethylene copolymer (C), and is preferably 20 parts by mass. 〇 1 to 15 parts by mass. The amount of the vulcanization aid to be used is not particularly limited, and is preferably from 1 to 10 parts by mass based on 1 part by mass of the rubber component. In the case of the branched conjugated diene-aromatic ethylene copolymer composition, softeners, fillers, heat stabilizers, antistatic agents other than the above may be used within the range not detracting from the object of the embodiment. Various additives such as weathering stabilizers, anti-aging agents, colorants, and lubricants. Specific examples of the filler include calcium carbonate, magnesium carbonate, aluminum sulfate, barium sulfate, and the like. As the heat stabilizer, the antistatic agent, the weathering stabilizer, the anti-aging agent, the colorant, and the lubricant, a known material can be used. 147412.doc -35- 201041914 [Examples] Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples. Further, the present invention is not limited to the following examples. The measurement methods and evaluation methods of the physical properties used in the examples and comparative examples are shown below. (1) The amount of bonded styrene is measured by using a UV-visible spectrophotometer (UV-2450 manufactured by Shimadzu Corporation) by UV-visible spectrophotometer (UV-2450 manufactured by Shimadzu Corporation). The amount of bonded styrene (mass%) was measured. (2) The microstructure of the dilute portion (the amount of the ethylene bond) The sample for the measurement is a carbon disulfide solution, and the solution pool is used, and the Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, FT_IR23〇) is used at 600. The infrared spectrum was measured within a range of ~1000, and the microstructure (ethylene bond amount) of the butadiene portion was determined by the equation of the method of Hampton by the absorbance at a specific wave number. (3) Mooney viscosity and Mooney relaxation rate The temperature was set to 12 根据 according to IS0289-1 and IS0289-4 using a Mooney viscometer (manufactured by Ueshima Seisakusho Co., Ltd., VRU32). Hey, the Mooney viscosity and the Mooney relaxation rate were measured. First, the sample was preheated at l2〇〇c for 1 minute, and then the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured, and it was set to the Mooney viscosity + . Then, 'the rotation of the rotor is stopped immediately, and the torque per 1.6 seconds after the stop is recorded in the Muni unit, and the slope of the straight line when the torque and time (seconds) are made into the double logarithm map is obtained. 'Set its absolute value to the Mooney relaxation rate (MSR). (4) Weight average molecular weight and molecular weight distribution 147412.doc -36 - 201041914 A chromatogram was measured using a GPC measuring device connected with three columns of polystyrene gel as a filler, based on the use of standard polystyrene The calibration curve is used to determine the weight average molecular weight. Further, the molecular weight distribution (weight average molecular weight / number average molecular weight) is determined from the ratio of the weight average molecular weight to the number average molecular weight. For the dissolving liquid, tetrahydrofuran (THF) was used. The column is protected by a column: Tosoh TSKguardcolumn HHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR. An RI detector (HLC8020 manufactured by Tosoh Corp.) was used under the conditions of an oven temperature of 40 ° C and a THF flow rate of 1.0 mL/min. A 10 mg sample for measurement was dissolved in 10 mL of THF to prepare a measurement solution, and 200 μM of the measurement solution was injected into a GPC measuring device for measurement. (5) Glass transition temperature (Tg) Measured according to IS022768: 2006, using DSC3200S manufactured by MAC Science. The DSC curve was recorded while heating at 20 ° C /min from -100 ° C under a flow of 50 mL / min of helium, and the Inflection point of the DSC differential curve was set to the glass transition temperature. (6) Conversion rate A polymer solution obtained by injecting about 20 mL of the outlet from the reactor into a 100 mL bottle sealed with 0.50 mL of n-propylbenzene as an internal standard and about 20 mL of benzene was prepared for the measurement. kind. The obtained sample was measured in a glass column chromatography (GC) equipped with a packed column carrying an Apiesson seal wax, according to a calibration curve of 1,3-butadiene monomer obtained in advance with styrene. The calibration curve of the monomer was used to determine the amount of residual monomer in the polymer solution, and the conversion ratio of 147412.doc -37-201041914 1,3-butadiene monomer and styrene monomer was determined. [Example 1] The internal volume of two chambers was 10 L, the ratio of the height (l) to the diameter (9) of the interior was (4), the inlet was provided at the bottom, the outlet was provided at the top, and the jacket and the temperature adjustment jacket were provided. The high pressure crucibles are connected in series, and the first block is set as a polymerization reactor, and the second block is set as a coupling reactor. U·butylene dilute, styrene, and hexanone, which previously removed impurities such as moisture, were mixed at a rate of addition of 23.8 g/min, U.9 g/min, and 187 5 g/min to prepare a mixed solution. The deactivation treatment of the impurities was carried out using a n-butyl clock (treatment of a positive T-base clock) at a rate of mmGi/min to the obtained mixed solution, and mixed using a static mixer. The mixed solution was continuously supplied to the bottom of the first polymerization reactor, and 2,2-bis(2-tetrahydrofuryl)propane as a polar substance was added at a rate of 〇〇14 g/min. The n-butyllithium of the starting agent is supplied to the bottom of the first polymerization reactor at a rate of 〇145 mm〇l/min, and the internal temperature of the outlet of the polymerization reactor (temperature of the copolymer solution) is controlled to 100 t. Polymerization. At this time, the average residence time in the reactor was 3 〇 minutes. The polymer solution was continuously taken out from the top of the first polymerization reactor and supplied to the bottom of the second-site coupling reactor. When the polymerization reaction in the first polymerization reactor is fixed, pay special attention not to contact with air. While discharging a small amount of the polymer solution from the inlet of the second coupling reactor, add about 1 mL of methanol to A mixed solution of cyclohexane of about 3 〇mL. And 'the antioxidant (BHT: 2,6-di-t-butyl-4-hydroxytoluene) was added to the mixed solution in a manner of 0.2 g per 100 g of the polymer to 1474 l2.doc -38 - 201041914 The solvent was removed by a barrel dryer to obtain a sample (co-diene-aromatic ethylene copolymer (I)) having a measured molecular weight and a Mooney viscosity and a Mooney relaxation rate. The Mooney viscosity and the Mooney relaxation rate were measured after 10 times of a 6 inch roller set to 1010 °C. Sample (co-monoolefin-aromatic ethylene copolymer (I)) 12 〇 °c

The viscosity (ML-I) was 93.5, the Mooney relaxation rate (MSR-I) was 〇·687, and the weight average molecular weight (Mw-I) of the I-diethyl-exchanged nose measured by GPC was 674,000. Further, the polymerization conversion rate at the inlet of the second-stage coupling reactor was 13-butadiene 〇 to 98%, and styrene was 96%. The temperature of the second coupling reactor was maintained at 85. Further, a coupling reaction was carried out by adding tetraglycidyl-1,3-diaminomethylcyclohexane from the bottom of the second-stage coupling reactor at a rate of addition of 184 mm 〇 1 minute. Tetraglycidyl-1,3-diaminomethylcyclohexane is a compound having four epoxy groups in a fluorene molecule, and the total number of moles of the functional groups and the number of moles of n-butyl groups added thereto The ratio (equivalent ratio) is 0_30. The Q polymer solution taken out from the top of the second coupling reactor was continuously added at a rate of 〇_〇71 g/min (positive hexane solution) at a rate of 0.2 g per 1 g of the polymer. The antioxidant (BHT) ends the coupling reaction. Thereafter, the solvent was removed to obtain a branched total di-hydrocarbon-aromatic ethylene copolymer (c). The coupled conjugated diene-aromatic ethylene copolymer (c) had a 120% Muini viscosity (ML-C) of 134.2 and a Mooney relaxation rate (MSR-C) of 0.401, as determined by GPC. The weight average molecular weight (Mw_C) in terms of polystyrene was 886,000, and the ratio of the weight average molecular weight to the number average molecular weight ((Mw_C) / (Mn-C)) was 2.32. Further, the amount of bonded styrene was 33 mass. /〇, 1474I2.doc •39· 201041914 The amount of ethylene bond (丨, 2_bond amount) in the butadiene bond unit is 34 mol%, and the glass transition temperature measured by DSC is _3rc. Further, in the branched conjugated diene-aromatic ethylene copolymer solution, S_RAe oil 〇/叩 叩 ; is added in an amount of 37.5 parts by mass per 100 parts by mass of the polymer; after the company manufactures 'NC_14 〇, The oil-repellent copolymer (sample a) was obtained by removing/treat. The properties of the obtained copolymer were not shown in Table 1. [Examples 2 and 3] Polymerization starting n-butyllithium, 2,2 bis(2-tetrahydrofuranyl)propane, and tetraglycidyl hydrazine, 3-diamino group were used under the conditions shown in Table 1. Mercaptocyclohexane. The other conditions were the same as in Example i to obtain an oil-extended copolymer (samples b, C). The properties of the obtained copolymer are shown in Table 丄. [Example 4] As shown in Table 2, 'the method of Example 1 did not change the ratio of 1,3-butadiene to styrene, and the supply amount of the monomer was changed, and the average residence time was set to 25 minutes. The internal temperature of the outlet of the reactor was set to 1 〇 5 t, and the supply enthalpy of other materials was also changed as shown in Table 1, and polymerization and coupling reactions were carried out. Thereafter, oil addition and solvent removal were carried out in the same manner as in Example 1 to obtain an oil-filled octamer (5 pattern d). The properties of the obtained copolymer are shown in Table 2. [Example 5] An oil-extended copolymer was obtained in the same manner as in Example 4 except that the addition amount of tetrakis(glyceryl)-1,3-diaminomethylcyclohexan was changed as shown in Table 2; (Sample e). The properties of the obtained copolymer are shown in Table 2. [Example 6] 147412.doc •40· 201041914 The polymerization initiated n-butyllithium, 2,2-bis(2-tetrahydrofuryl)propane and tetraglycidyl-1,3-diaminomethylcyclohexane. The amount of the alkane added is shown in Table 2. The other conditions were the same as in Example 4, and an oil-extended copolymer (sample f) was obtained. The properties of the obtained copolymer are shown in Table 2. [Comparative Example 1] As shown in Table 3, 'the ratio of 3-butadiene to styrene was not changed from the method of Example 1, and the supply amount of the monomer was changed, and the average residence time was set to 〇45. In minutes, the internal temperature of the outlet of the reactor was set to 9 〇〇c, and the supply amount of other substances was also changed as shown in Table 1, and polymerization reaction and coupling reaction were carried out. Thereafter, oil addition and solvent removal were carried out in the same manner as in Example 1 to obtain an oil-extended copolymer (sample g). The properties of the obtained copolymer are shown in Table 3. [Comparative Example 2] As shown in Table 3, the addition amount of n-butyllithium and 2,2-bis(2-tetrahydrofuranyl)propane was changed, and tetraglycidyl-di-diamine fluorenyl group was further added. The addition of hexane was set to 〇. The polymerization reaction was carried out by using the same conditions as in the comparative example o, and the polymerization reaction was carried out. Thereafter, oil addition and solvent removal were carried out in the same manner as in Example i to obtain an oil-extended copolymer (sample h). In Examples 1 to 4 and Comparative Examples! In, use! In the reactor, a polymerization reaction was carried out. In contrast, in Comparative Example 2, a polymerization reaction was carried out using a two-stage reactor. The polymerization conversion ratio was measured using a ruthenium polymer solution obtained from the top of the second reactor. The properties of the obtained copolymer are shown in Table 3. Eight [Example 7] = Table 4 shows that the ratio of L3-butadiene to styrene was changed from the method of Example ,, and the supply amount of the monomer was changed, and the average residence time was set to 25 minutes 147412.doc -41 · 201041914, the internal temperature of the reactor outlet was set to 97 ° C, and the amount of other substances was changed to carry out polymerization and coupling reaction, and then oil addition and solvent removal were carried out in the same manner as in Example 1 to obtain oil-extended copolymerization. (sample i). The properties of the obtained copolymer are shown in Table 4. [Examples 8 and 9] The polymerization amount of n-butyllithium, 2,2-bis(2-tetrahydrofuryl)propane, and tetraglycidyl-1,3-diaminomethylcyclohexane was increased. Table 4 shows. The other conditions were the same as in Example 7 to obtain an oil-extended copolymer (samples j, k). The properties of the obtained copolymer are shown in Table 4. [Example 10] As shown in Table 5, the ratio of 13-butadiene to stupid ethylene was not changed from the method of Example 7, and the supply amount of the monomer was changed, and the average residence time was set to 22 minutes. The internal temperature of the outlet of the device was set to 1 〇 2, and the supply amount of other substances was also changed as shown in Table 1, and polymerization and coupling reactions were carried out. Thereafter, oil addition and solvent removal were carried out in the same manner as in Example 1 to obtain an oil-extended copolymer (Sample 1). The properties of the obtained copolymer are shown in Table 5. [Comparative Example 3] As shown in Table 5, the addition amount of tetraglycidyl-I, % bisaminodecylcyclohexane was reduced from the method of Example 7. The other conditions were the same as in Example 7 to obtain an oil-extended copolymer (sample m). The properties of the obtained copolymer are shown in Table 5. [Comparative Example 4] As shown in Table 5, the ratio of 3-butadiene to stupid ethylene was not changed from the method of Example 7, and the supply amount of the monomer was changed 'the average residence time was set to 1474l2. D〇c -42· 201041914 45 minutes, the internal temperature of the reactor outlet was set to 90 ° C, and the supply amount of other substances was also changed as shown in Table 5, and polymerization and coupling reaction were carried out. Thereafter, oil addition and solvent removal were carried out in the same manner as in Example 7 to obtain an oil-extended copolymer (sample η). The properties of the obtained copolymer are shown in Table 5. [Table 1]

Example 1 Example 2 Example 3 Sample No. abc 1,3-butadiene (g/min) 23.8 23.8 23.8 Styrene (g/min) 11.9 11.9 11.9 n-hexane (g/min) 187.5 187.5 187.5 Polymerization Temperature (°C) 100 100 100 Poly-n-butyllithium (mmol/min) 0.100 0.100 0.100 Polymerization starting n-butyl hydrazine (mmol/min) 0.145 0.158 0.182 pieces of polar substance “addition amount (g/min) 0.014 0.015 0.017 TGAMH*2 Addition amount (mmol/min) 0.0184 0.0192 0.0211 Lithium equivalent ratio 0.30 0.30 0.30 Average residence time (1st reactor) (minutes) 30 30 30 Monomer concentration (% by mass) 16 16 16 Polymerization conversion Rate 1,3-butadiene (%) 98 99 99 Stupid ethylene (%) 96 98 99 Bonded styrene amount (% by mass) 33 33 33 Ethylene bond amount (1, 2-bond amount) (mol% 34 34 34 Glass Transfer Temperature (°C) -31 •31 -31 Weight average molecular weight (Mw-I) (104 g/mol) 67.4 62.5 57.3 Pre-coupling polymer analysis value 120°C Mooney viscosity (ML- I) {260-(ML-I)}/300 93.5 0.555 82.4 0.592 70.8 0.631 Value {310-(ML-I)}/300 0.722 0.759 0.7 97 120 °c Mooney relaxation rate (MSR-I) 0.687 0.724 0.772 Weight average molecular weight (Mw-C) (104 g/mol) 88.6 79.0 71.3 (Mw-C)/(Mn-C) 2.33 2.37 2.zs After coupling (final) poly 120 ° C Mooney viscosity (ML-C) 134.2 120.4 108.9 Analysis value [214-(ML-C)}/300 0.266 0.312 0.350 [260-(ML-C)}/300 0.419 0.465 0.504 120 °c Mooney relaxation rate (MSR-C) 0.401 0.448 0.478 *12,2-bis(2-tetrahydrofuryl)propane*2 tetraglycidyl-1,3-diaminomethylcyclohexane -43-147412.doc 201041914 [Table 2] Example 4 Example 5 Example 6 Sample is 0. def 1,3-butadiene (g/min) 28.6 28.6 28.6 Styrene (g/min) 14.3 14.3 14.3 Hexane (g/min) 225.1 225.1 225.1 Polymerization temperature (°C) 105 105 105 Polybutyl n-butyllithium (mmol/min) 0.120 0.120 0.120 Polymerization starting n-butyllithium (mmol/min) 0.185 0.185 0.200 pieces of polar substance 41 added amount (g/min) 0.025 0.025 0.027 TGAMH*2 Addition amount (mmol/min) 0.0133 0.0236 0.0248 Clock equivalent ratio 0.17 0.31 0.31 Average residence time (1st reaction (min) 25 25 25 Monomer concentration (% by mass) 16 16 16 Polymerization conversion 1,3-butadiene (%) 98 98 99 Styrene (%) 97 97 98 Bonded styrene amount (% by mass 33 33 33 Ethylene bond amount (1,2-bond amount) (mol%) 34 34 34 Glass transition temperature Cc) -31 -31 -31 Weight average molecular weight (Mw-I) (104 g/mol) 67.9 67.9 62.7 Pre-coupling polymer 120 °C Mooney viscosity (ML-I) 86.2 86.2 73.4 Analysis value {260-(ML-I)}/300 0.579 0.579 0.622 Value {310-(ML-I)}/300 0.764 0.764 0.789 120°C Mooney relaxation rate (MSR-I) 0.667 0.667 0.715 Weight average molecular weight (Mw-C) (104 g/mol) 79.6 87.3 75.9 (Mw-C)/(Mn_C) 2.48 2.42 2.35 After coupling (Final) Polymerization 120 °C Mooney Viscosity (ML-C) 119.5 128.2 115.4 Mirror not T value [214-(ML-C)}/300 0.315 0.286 0.329 [260-(ML-C)}/300 0.468 0.439 0.482 *10 120 °C Mooney relaxation rate (MSR-C) 0.422 0.372 0.409 ” 2,2_double (2-3⁄43⁄43⁄4 *2 tetraglycidyl-i,3-diaminodecylcyclohexane •44 - 147412.doc 201041914 [Table 3] Comparative Example 1 Comparative Example 2 Sample No. hg 1,3-butadiene (g/min) 16.0 16.0 Styrene (g/min) 8.0 8.0 Hexane (g/min) 125.6 125.6 Polymerization temperature (°C) 90 90 Polybutyl n-butyllithium (mmol/min) 0.067 0.067 Initial n-butyl lithium (mmo丨 / min) 0.100 0.090 pieces of polar substance "addition amount (g / min) 0.0070 0.0065 TGAMH * 2 addition amount (mmol / min) 0.0125 - lithium equivalent ratio 0.30 - average residence time (1st block Reactor) (minutes) 45 45 Monomer concentration (% by mass) 16 16 Polymerization conversion 1,3-butadiene (%) 98 99 Styrene (%) 95 99 Bonded styrene amount (% by mass) 33 33 Ethylene bond amount (1,2-bond amount) (mol%) 34 34 Glass transition temperature (°C) -31 -31 Weight average molecular weight (Mw-ΐχΐΟ4 g/mol) 63.4 - yV 120°C Mooney viscosity (ML-I) 85.4 - 77 LY before coupling polymer analysis value {260-(ML-I)}/300 0.582 - value {310-(ML-I)}/300 0.749 - 120°C Rate (MSR-I) 0.785 Weight average molecular weight (Mw-C) (104 g/mol) 82.3 71.2 (Mw-C)/(Mn-C) 2.30, 2.12 After coupling (final) Polymer analysis 120 °C Muni sticky (ML-C) 124.3 115.3 Value [214-(ML-C)}/300 0.299 0.329 [260-(ML-C)}/300 0.452 0.482 120°C Mooney relaxation rate (MSR-C) 0.498 0.712 * 1 2,2-bis(2-tetrahydrofuryl)propane*2 tetraglycidyl-1,3-diaminomethylcyclohexane

• 45· 147412.doc 201041914 [Table 4] Example 7 Example 8 Example 9 Sample No. ijk 1,3-butadiene ~~~ (g/min) 31.2 31.2 31.2 Styrene & (g/ Minutes) 17.1 17.1 17.1 n-hexane ~~~ (g/min) 220.1 220.1 220.1 Polymerization temperature ~~~~ (°C) 97 97 97 Treatment of n-butyl chain polymerization ------ (mmol/min) 0.136 0.136 0,136 Poly-polymerization of n-butyllithium (mmol/min) 0.218 0.200 0.185 ΊΤ Polar substance “addition amount ------__^ (g/min) 0.043 0Ό40 0.038 TGAMH*2 Addition amount (mmol/min) 0.0292 0.0277 0.0265 ---— Lithium equivalent ratio 0.33 0.33 0.33 Average residence time (1st reactor) (minutes) 25 25 25 Monomer concentration (% by mass) 18 18 18 Polymerization conversion ratio 1,3-butadiene (%) 99 99 99 Stupid ethylene (%) 98 98 98 Bonded styrene amount (% by mass) 35 35 35 Ethylene bond amount (1,2-bond amount) (mol%) 40 40 40 Glass transition temperature CC) -21 -21 -21 Weight average molecular weight (Mw-I) (104 g/mol) 59,0 63.8 68.2 yV 120 °C Mooney viscosity (ML-I) 66.6 77.2 83.2 77 k Coupling Polymer analysis value {260-(ML-I)}/300 0.645 0.609 0.589 Value {310-(ML-I)}/300 0.811 0.776 0.756 120°C Mooney relaxation rate (MSR-I) 0.692 0.671 0.636 Weight Average molecular weight (Mw-C) (10 g/mol) 78.5 82.4 86.1 (Mw-C)/(Mn-C) 2.35 2.32 2.28 After coupling (final) polymer 120 °C Mooney viscosity (ML-C) 106.6 116.0 122.6 Analysis [214-(ML-C)}/300 0.358 0.327 0.305 [260-(ML-C)}/300 0.511 0.480 0.458 120°C Mooney relaxation rate (MSR-C) 0.401 0.362 0.348 *1 2,2-bis(2-tetrahydrofuryl)propane*2 tetraglycidyl-1,3-diaminomethylcyclohexane 147412.doc -46- 201041914 [Table 5] Example 10 Comparative Example 3 Comparative Example 4 Sample No. 1 m η 1,3-butadiene (g/min) 35.4 31.2 17.3 Styrene (g/min) 19.4 17.1 9.5 Normally calcined (g/min) 250.2 220.1 122.0 Polymerization temperature (°C) 102 97 90 Poly-n-butyllithium (mmol/min) 0.154 0.136 0.075 Polymerization starting n-butylzyl (mmol/min) 0.240 0.218 0.122 piece of polar substance "addition amount (g/min) 0.049 0.043 0.021 TGAMH*2 Addition amount (mmol/min ) 0.0345 0.0053 0.0492 Lithium equivalent ratio 0.35 0.06 1.00 Average residence time (1st reactor) (minutes) 22 25 45 Monomer concentration (% by mass) 18 18 18 Polymerization conversion ratio 1,3-butadiene (%) 99 99 99 Benzene (%) 99 98 97 Bonding amount of ethylene (% by mass) 35 35 35 Ethylene bond amount (1,2-bond amount) (mol%) 40 40 40 Glass transition temperature (°c) 21 -21 -21 Weight average molecular weight (Mw-I) (l 04 g/mol) 59.7 59.0 65.2 and 120 °C Mooney viscosity (ML-I) 72.4 66.6 78.2 Analysis value of polymer before coupling {260-(ML- I)}/300 0.625 0.645 0.606 Value {310-(ML-I)}/300 0.792 0.811 0.773 120°C Mooney relaxation rate (MSR-I) 0.655 0.692 0.698 Weight average molecular weight (Mw-C) (104 g /mol) 81.0 68.2 91.2 (Mw-C) / (Mn-C) 2.42 2.38 2.15 After coupling (final) polymer 120 ° C Mooney viscosity (ML-C) 119.6 89.2 145.3 Analysis value [214-(ML- C)}/300 0.315 0.416 0.229 [260-(ML-C)}/300 0.468 0.569 0.382 120°C Mooney relaxation rate (MSR-C) 0.335 0.508 0.261 *1 2,2-bis(2-tetrahydrofuranyl) Propane*2 tetraglycidyl-1,3-diaminomethyl ring Alkyl

-47-147412.doc 201041914 [Examples 11 to 16] [Comparative Examples 5 to 8] The samples (samples a, b, d, e, g 丨, Ηη) shown in the above Tables 1 to 5 were set. As the raw material rubber, a rubber composition containing the raw material rubber was obtained according to the formulation shown below. Oil-filled styrene-butadiene copolymer (samples a, b, d, e, g~i, 1~n): 96.25 parts by mass • Polybutadiene rubber with a high 1,4-cis content (hereinafter, it is called high-poly butadiene rubber) (manufactured by Ube Industries, UBEPOL BR-150, 98% cis bond) ··········································· 00 parts by mass • Carbon black (N339 manufactured by Tokai Carbon): 5.00 parts by mass • decane coupling agent (Si75 manufactured by Degussa): 6.00 parts by mass • S-RAE oil (J〇M〇Process NC140 manufactured by Japan Energy Corporation): 15.75 parts by mass. Zinc white: 2.50 parts by mass • Stearic acid: 2.00 parts by mass. Wax (selective specific gangrene manufactured by Okinawa Chemical Co., Ltd.): 15 parts by mass • Anti-aging agent (Ν-isopropyl- Ν1-Phenyl-p-phenylenediamine): 2. 〇〇 parts by mass • Sulfur: 2.20 parts by mass • Vulcanization accelerator (Ν-cyclohexyl, 2-benzothiazolylsulfonamide): 17 parts by mass • Vulcanized Accelerator (diphenyl hydrazine): 2.00 parts by mass in total: 241.90 parts by mass The method of kneading the rubber composition is shown below. Using a closed kneading machine with a temperature control device (content amount 〇3 L), 147412.doc • 48· 201041914 is the first stage of mixing, under the condition of 72% filling rate and 7-degree rotor speed, mixing raw materials Rubber (samples a, b, d, e, g~i, m cis-butadiene rubber), silica dioxide, organic stone sinter coupling agent, processing/playing, controlling the temperature of the closed mixer, The discharge temperature (mixture) was 155 to 160 ° C to obtain a rubber composition. Secondly, as the second stage of the kneading, after the above-obtained formulation is cold "P to /JD·, add carbon black, white, stearic acid, wax, anti-aging agent into ❹ π . At this time, the discharge temperature (preparation) was also adjusted to 155 to 16 generations by temperature control of the mixer. After cooling, as a mixing stage of the third stage, sulfur and stone desiccant accelerators were added to the open drum of S C. Thereafter, it was molded and cured at 16 (TC) by a vulcanization press for 20 knives. After vulcanization, the physical properties of the rubber composition were measured. The physical property measurement results are shown in the following Tables 6 and 7. The rubber was measured by the following method. Physical properties of the composition (1) Binding rubber amount Q The formulation after the end of the second stage mixing step (about 2.2 g) is cut into a shape of about i mm square and placed in a Harris basket (Harris, ι〇) The weight was measured in a wire mesh system. Thereafter, it was dried in toluene at 23. After immersing for 24 hours, the drying treatment was carried out to measure the weight of the non-dissolved component of the benzene. Calculating the weight of the rubber (branched conjugated diene-aromatic ethylene copolymer + high-cis-butadiene rubber) bonded to the filler, and determining the ratio of the rubber combined with the filler to the amount of rubber in the initial formulation (2) Formulation Muney viscosity 147412.doc •49· 201041914 Using a Mooney viscometer, according to JIS K6300-1, after preheating at 130 ° C for 1 minute, 2 revolutions per minute (2 rpm) The rotor was rotated and the viscosity after 4 minutes was measured. The value of the Mooney viscosity The smaller the amount, the smaller the energy consumption during kneading, and the better the workability. (3) The tensile strength was measured according to the tensile test method of JIS K625 1. In Examples 11 to 14 and Comparative Example 5, Comparative Example 6 was set. 1 and indexed, Examples 15, 16 and Comparative Example 8 were indexed by setting Comparative Example 7 to 1 。. (4) The viscoelastic parameters were measured using a viscoelasticity tester (ARES) manufactured by Rheometrics Scientific. The viscoelastic parameters were measured in a torsion mode. For each of the measured values, Examples Π to 14 and Comparative Example 5 were indexed by comparing Comparative Example 6 to 1 ,, and Examples 15 and 16 and Comparative Example 8 were Comparative Example 7. It is set to 1 〇〇 and is indexed. Tan5 (loss tangent) measured at a frequency of 10 Hz and a strain of 1% is used as an index of wet skid resistance. The larger the value, the better the wet skid resistance. In addition, the frequency is 1 〇 Hz at 50 ° C, and the strain is 3. The measured enthalpy is (loss tangent) as an indicator of fuel economy characteristics. The smaller the value, the better the low hysteresis loss. G measured under the same conditions, (storage elastic modulus is set as an indicator of steering stability. The larger the value The higher the rigidity, the higher the stability (5) The wear resistance is measured by the Akron abrasion tester (Yaoda Seiki Co., Ltd.: the load is measured..., the amount of wear is changed.) 丄: t 乂 Example 5 sets Comparative Example 6 to 100 On the other hand, the indexing of Examples 15, 16 I47412.doc-50-201041914 and Comparative Example 8 was indexed by setting Comparative Example 7 to 100. The larger the index, the more excellent the sharpness is. [Table 6] Example 11 Example 12 Example 13 Example 14 Comparative Example 5 Comparative Example 6 Oil-filled styrene-butadiene copolymer abdegh Formulation Muney viscosity 55 52 53 54 54 61 Bonding rubber amount (%) 46 44 43 45 42 39 Vulcanized rubber Physical Property Tensile Strength Index 108 103 102 107 104 700 Abrasion Resistance Index 108 104 103 107 102 100 0°C tan8 Index (strain 1%) 100 102 99 100 100 100 50°C tan8 Index (strain 3%) 95 97 97 95 98 100 50°CG' index (strain 3%) 97 98 98 97 98 100

[Table 7] Example 15 Example 16 Comparative Example 7 Comparative Example 8 Oil-filled styrene-butadiene copolymer i 1 m η Formulation Muney viscosity 46 49 45 58 Binding rubber amount (%) 42 45 37 54 Vulcanized rubber Tensile strength index 105 107 100 110 Abrasion resistance index 105 108 100 115 0°C tan5 index (strain 1%) 103 103 100 101 50°C tan6 index (strain 3%) 98 96 100 92 50°C G ' Index (strain 3%) 99 98 100 94 -51 - 147412.doc 201041914 will use micro, .,. The structure (bonded styrene amount and ethylene bond amount) is an equivalent of the oil-filled exemplified copolymer and the comparative example is compared with the comparative example and the copolymer of Comparative Example 1 which is polymerized at a low temperature is considered. g does not sufficiently branch, so the main condition of the above formula (1) is not satisfied. From Examples 1 to 6 of Comparative Table 3 and Comparative Example 1, it is understood that the copolymers a to f of Examples 1 to 6 have a shorter retention time in the reactor for obtaining a sufficient polymerization conversion ratio than the comparative example. The co-construction g of 1 is excellent in productivity. Further, the rubber compositions of Examples 1 to 14 were superior to Comparative Example 5 in the balance between properties such as tensile strength, abrasion resistance, low hysteresis loss resistance, and wet skid resistance, and workability. The copolymer of Comparative Example 2 which was polymerized without being subjected to the coupling reaction was insufficient, and the main conditions of the formula (1) were not satisfied. Regarding the use of Examples J i to i 4 of the copolymers a, b, d, and e of Examples 1 2 and 4, compared with Comparative Example 6 using the copolymer h of Comparative Example 2, the viscosity of the formulation was better than that of Comparative Example 6 Low, good processability, by 5 〇. 〇 and 〇. It is known that the balance between low hysteresis loss and wet skid property is excellent, tensile strength and abrasion resistance are also good, and practically sufficient wear resistance and damage characteristics are also satisfied. The copolymer of Comparative Example 3 had a smaller weight average molecular weight and a lower Mooney viscosity. The copolymers of Examples 8, 11 and Examples 15, 16 of Example 1 and the copolymer of Comparative Example 3 were used. In Comparative Example 7, it was found that the tans of 5 〇 and 〇 °C showed that the balances of the low hysteresis loss and the wet skid resistance of Examples 15 and 16 were excellent, and the tensile strength and the abrasion resistance were also good, and the utility model was also satisfactory. Full wear resistance and damage characteristics. Comparative Example 4 of Comparative Example 4 used for polymerization at a lower temperature to improve coupling efficiency 147412.doc -52 - 201041914 Comparative Example 8 of Comparative Copolymer η, Comparative Examples 7 to 10 In comparison with Comparative Example 4, it was found that the residence time in the reactor for obtaining a sufficient polymerization conversion ratio was long. Thus, it was found that the copolymer n of Comparative Example 4 was inferior in productivity compared with Examples 7 to 10, The copolymerization of the rubber composition of Comparative Example 8 was high, and the workability of the rubber composition was higher than that of Examples 15 and 16. The application was based on April 7, 2009. The application of this patent office in the case of the 利本中利中4 (Japanese Patent Special Purpose 2__93252), The contents thereof are incorporated in the present specification as a reference. [Industrial Applicability] The total of 1⁄4 di-hydrocarbon-aromatic ethylene copolymer of the present invention has industrial properties as a material for tire surfaces, shoes, industrial articles, and the like. Availability. 〇147412.doc •53-

Claims (1)

201041914 VII. Patent application scope: 1. A branched conjugated diene-aromatic ethylene copolymer (c) which is a random copolymer; aromatic ethylene in the above conjugated diene/aromatic ethylene copolymer The amount of bonding is 30 to 38% by mass, and the amount of ethylene bonded in the total bonding unit of the conjugated diene is from 3 to 43 mol%, and the conjugated diene-aromatic ethylene copolymer (C) is used. The polystyrene-equivalent weight average molecular weight (Mw-C) obtained by gel permeation chromatography (GPC) is 700,000 to 1,000,000, and the weight average molecular weight (Mw-C) is relative to the number average molecular weight (Mn-C). The ratio ((Mw-C) / (Mn_C)) is 1.7 to 3.0, and the Moi viscosity (ML-C) and the Mooney relaxation rate (MSR-C) measured at 120 ° C satisfy the following formula (1) Relationship, {214-(ML-C)}/300$ (MSR-C)S {260-(ML-C)}/300...(1) (in equation (1), 100S (ML-C) ) S140). 〇2. The branched conjugated diene-aromatic ethylene copolymer of claim 1, which is a polyfunctional modifier having four or more functional groups, such as the following conjugated diene-aromatic ethylene When the copolymer (I) is coupled, the conjugated fluorene diene-aromatic ethylene copolymer (I) has a polystyrene-equivalent weight average molecular weight (^^ rating -1) of 500,000 to 700,000 at 120 ° ( : The measured Mui viscosity (ML-I) and the Munni relaxation rate (MSR-I) satisfy the relationship of the following formula (2), {260-(ML-I)}/3 00^ (MSR-I) ^ {3 10-(ML-I)}/3 00··· (2) 147412.doc 201041914 (in the formula (2), 65$ (ML-I)g 100). 3. A branch-like vehicle A dilute hydrocarbon-aromatic ethylene copolymer composition comprising the branched conjugated diene-aromatic ethylene copolymer (C) according to claim 1 or 2 and an inorganic filler. 4. A branched conjugate A method for producing a branched conjugated diene-aromatic ethylene copolymer (C) according to claim 1 or 2, which comprises the following steps: Conjugated diolefin compound, aromatic a step of continuously supplying a solution of a group of a vinyl compound and an anionic polymerization initiator to a reactor and subjecting it to a polymerization reaction to obtain a solution of a conjugated diene-aromatic ethylene copolymer having an active terminal; The polyfunctional modifier having four or more functional groups reactive with the above-mentioned active terminal reacts the above-mentioned conjugated diene-aromatic ethylene copolymer. 5. The branched conjugated diene-aromatic acetylene copolymer A method for producing a branched conjugated diene-aromatic ethylene copolymer (C) according to claim 1 or 2, which comprises the steps of: a reactor equipped with a mixer a step of continuously supplying a solution containing a total consumption of a dilute smoke compound, an aromatic ethylene compound, and an anionic polymerization initiator, and subjecting it to a polymerization reaction; and exporting from the above-mentioned reaction benefits continuously to the media Step of having a solution of a conjugated diene-aromatic ethylene copolymer having an active terminal, using a plurality of members having four or more functional groups capable of reacting with the above-mentioned active terminal The modifier can be used to copolymerize the above-mentioned co-dop hydrocarbon-aromatic ethylene copolymer I47412.doc 201041914. In the above polymerization reaction, the internal temperature of the reactor outlet is maintained at 95-11 〇°n. The polymerization reaction is continuously carried out with an average residence time ί of 5 minutes or more and 35 minutes or less. 6. For example, the k-process of the branched-type co-worker-aromatic ethylene copolymer of the claim 4 or 5, wherein the above polyfunctional modification is carried out The above polyfunctional modifier is used in such a manner that the total number of moles of the functional groups of the agent is 5 times the molar number of the above anionic polymerization initiator. 〇147412.doc .201041914 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the feature: (none) 147412.doc