MXPA06006539A - Vinyl-cis-polybutadiene rubber and butadiene rubber composition using same - Google Patents

Abstract

Disclosed is a vinyl-cis-polybutadiene rubber which contains 1,2-polybutadiene and a polymer material having a melting point lower than that of 1,2-polybutadiene wherein at least one unsaturated double bond is contained per one repeating unit. The vinyl-cis-polybutadiene rubber is characterized in that 1,2-polybutadiene and the polymer material are dispersed in a cis-polybutadiene rubber as the matrix component of the vinyl-cis-polybutadiene rubber in such a state that 1,2-polybutadiene and the polymer material are physically and/or chemically adsorbed to each other. Also disclosed is a method for producing such a vinyl-cis-polybutadiene rubber. Consequently, there can be provided a vinyl-cis-polybutadiene rubber having a small die swell ratio, excellent extrusion processability and workability which enables to obtain a vulcanized product exhibiting excellent characteristics required for the side/tread of tires.

Description

COMPOSITION OF VINIL-CIS-POLYBUTADIENE AND BUTADIENE RUBBER AND USE OF THE SAME Field of the Invention The present invention relates to a novel vinyl-cis-polybutadiene rubber produced by permitting consecutively 1,2-polybutadiene of a high melting point of 170 ° C or more and polyisoprene or polybutadiene of a melting point. low and that is dispersed in the cis-polybutadiene rubber matrix. In addition, the present invention relates to a butadiene rubber composition utilizing vinyl cis-polybutadiene rubber. Background of the Invention In the molecular chain of polybutadiene, there exists consecutively a binding portion generated by the 1,4 polymerization (structure 1,4) and a binding portion generated by the 1,2 polymerization (structure 1,2) which is called microstructure. The structure 1,4 is divided into two types of structure, that is, the cis structure and the trans structure. Alternatively, the structure 1,2 takes a structure with the vinyl group as a side chain. In the related art a method has been carried out to produce a vinyl cis-polybutadiene rubber composition in inert organic solvents, such as aromatic hydrocarbons, such as benzene, toluene and xylene and halogenated hydrocarbons thereof, for example, chlorobenzene. However, when solvents are used, such as aromatic hydrocarbons and halogenated hydrocarbons, the resulting polymerization solution has such a high viscosity that agitation, heat transfer and heat transfer are difficult, which requires excessive energy to the recovery of the solvent. Additionally, solvents such as aromatic hydrocarbons and halogenated hydrocarbons are very dangerous to the environment, due to toxicity and carcinogenesis. As the production method, a method is known which includes a step of producing a cis-polybutadiene rubber by the cis-1,4 polymerization of 1,3-butadiene using a catalyst obtained from water, a soluble cobalt compound and a chloride of organic aluminum represented by the general formula A1RnX3-n (provided that R is an alkyl group of one to 6 carbon atoms, phenyl group or cycloalkyl group, X is a halogen element, and n is a number of 1.5 to 2) in the inert organic solvent and a 1,2-syndiotactic polymerization step (hereinafter abbreviated as "1,2-polymerization") of 1,3-butadiene in the presence of a 1.2 syndiotactic polymerization catalyst obtained from a cobalt compound Soluble, an organic aluminum compound represented by the general formula A1 R3 (provided that R is an alkyl group of one to 6 carbon atoms, phenyl group or cycloalkyl group) and carbon disulfide, with or without the addition of 1, 3-butadi ene and / or solvent for the resulting polymerization system (see for example, J P-B-49-6666 (patent reference 1), and J P-B-49-1,7667 (patent reference 2)). Additionally, for example, documents J PB-62-1 71 (patent reference 3), J PB-63-36324 (patent reference 4), JP-B-2-37927 (patent reference 5), JP- B-2-38081 (patent reference 6) and J PB-3-63566 (patent reference 7) describe a method that includes the production step for a vinyl-cis-polybutadiene rubber composition by a cis-polymerization. 1, 4 of 1, 3-butadiene in the presence or absence of carbon disulfide and methods that include a step for the separation and recovery of 1,3-butadiene and carbon disulfide to recycle 1,3-butadiene substantially so that it never contains carbon dioxide and the inert organic solvent. In addition, J PB-4-4881 5 (patent reference 8) discloses a composition of hle with a small proportion of h inchading in the die of the composite material, of which the vulcanized product has an excellent tensile strength and A great resistance to bending-breaking-growing preferably as the sidewall of a rim. Additionally, document JP-A-2000-44633 (patent reference 9) describes a method for the production of vinyl-cis-polybutadiene rubber in an inert organic solvent containing C4 distillates, such as n-butane, cis-2-butene, trans-2-butene and butene- 1 as the main components. JP-A-2000-44633 discloses that the 1,2-polybutadiene contained in the rubber composition according to the method is a short fiber glass, wherein 98% or more of the length of the fiber is less than 0.6 μm in the distribution of the crystal in the short fiber along the main axis; and 70% more of it is less than 0. 2 μm and that the resulting rubber composition has an improved molding ability of cis-1,4-polybutadiene, tension stretching, tensile strength and a flexural-break-grow resistance. However, a rubber composition with several improved properties has been sued for some use. Patent Reference 1: JP-B-49-17666 Patent Reference 2: JP-B-49-17667 Patent Reference 3: JP-B-62-171 Patent Reference 4: JP-B-63-36324 Patent 5: JP-B-2-37927 Patent Reference 6: JP-B-2-38081 Patent Reference 7: JP-B-3-63566 Patent Reference 8: JP-B-4-48815 Patent Reference 9 : JP-A-2000-44633 Summary of the Invention It is an object of the present invention to provide a vinyl cis-polybutadiene rubber having a rubber composition that provides a butadiene rubber composition with a small proportion of swelling in the rubber. and an excellent extrusion processing and operation capacity for the production of rims, which exerts excellent properties of resistance to breakage, resistance to abrasion and resistance to sliding friction, as well as a very high resistance to bending. break-growth and high rigidity, when the butadiene rubber composition is vulcanized. It is an object of the present invention to produce a butadiene rubber composition with excellent properties, particularly a butadiene rubber composition for a rim. The present invention has achieved the objects by means of the following constitutions. 1. A rubber of vinyl-cis-polybutadiene containing 1,2-polybutadiene and a polymer substance with a melting point lower than that of 1,2-polybutadiene and with at least one unsaturated double bond per unit of repetition, wherein the 1,2-polybutadiene and the polymer substance are dispersed under conditions physically and / or chemically adsorbed to the rubber of cis-polybutadiene as the matrix component of the vinyl cis-polybutadiene rubber. 2. The vinyl-cis-polybutadiene rubber as described in item 1 above, wherein the 1,2-polybutadiene and the polymer substance are dispersed in short crystal fibers and / or particles in the rubber of cis-polybutadiene as the rubber matrix component of vinyl-cis-polybutadiene. 3. The vinyl-cis-polybutadiene rubber as described in item 1 or 2 above, wherein the 1,2-polybutadiene is 1,2-polybutadiene of a melting point of 170 ° C or greater and the substance of The polymer is at least one selected from polyisoprene, crystallizable polybutadiene with a melting point of 150 ° C or less, liquid polybutadiene and derivatives thereof. 4. The vinyl-cis-polybutadiene rubber described in any of items 1 to 3 above, wherein the unsaturated polymer substance is contained within the range of 0.01% to 50% by mass to the total of the glass fiber of the 1,2-polybutadiene and the cis-polybutadiene rubber. 5. The vinyl-cis-polybutadiene rubber described in any of items 1 to 4, wherein the viscosity of the cis-polybutadiene rubber as the matrix component in toluene solution at 25 ° C is within a range from 10 to 6. The vinyl-cis-polybutadiene rubber described in any of the points from 1 to 5, where [?] of the cis-polybutadiene rubber as the component of the matrix is within a range of 1.0 to 5.0. 7. The vinyl-cis-polybutadiene rubber described in any of points 1 to 6, wherein the content of the 1,4-cis structure of the cis-polybutadiene rubber as a matrix component is within a range of 80% by mass or greater. 8. The vinyl cis-polybutadiene rubber described by any of items 1 to 7 above, wherein the Mooney viscosity of the cis-polybutadiene rubber as the component of the vinyl-cis-polybutadiene rubber matrix is found in a range of 10 to 50. 9. The vinyl-cis-polybutadiene rubber described in any of points 1 to 8 wherein the polymer substance is an insoluble material in the boiling of n-hexane. 10. The vinyl-cis-polybutadiene rubber described in any of points 1 to 9, wherein the 1,2-polybutadiene is dispersed in short crystal fibers in the rubber of cis-polybutadiene as a component of the rubber matrix. of vinyl-cis-polybutadiene and the polymer substance is dispersed in the particles thereof and wherein the short crystal fiber of 1,2-polybutadiene is dispersed in the particle of the polymer substance. 11. The vinyl-cis-polybutadiene rubber described in item 10 above, wherein the short crystal fiber of 1,2-polybutadiene is never contained in the particle of the polymer substance, but is also dispersed in the rubber of cis- polybutadiene as the component of the matrix, and wherein the length of the short glass fiber dispersed in the matrix along the main axis is within a range of 0.2 to 1,000 μm and the length of the short glass fiber of the 1, 2-polybutadiene dispersed in the particle of the polymer substance along the main axis is within a range of 0.01 to 0.5 μm. 12. A butadiene rubber composition prepared by composing the vinyl cis-polybutadiene rubber described in item 1 or 2 above from 10 to 300 parts by weight per 100 parts by weight of a rubber selected from natural rubber, polyisoprene rubber, rubber of styrene-butadiene copolymer or rubber mixtures of at least two types thereof. 13. A butadiene rubber composition for tires, wherein the vinyl cis-polybutadiene rubber described in points 1 to 11 above and / or the butadiene rubber composition described in item 3 above are used. 14. A method for producing a vinyl-cis-polybutadiene rubber by a cis-1,4 polymerization step in 1,3-butadiene using a cis-1,4 polymerization catalyst in a hydrocarbon series solvent, one step of polymerization 1, 2 of 1,3-butadiene in the concurrent presence of a polymerization catalyst 1, 2 in the resulting polymerization mixture to generate 1,2-polybutadiene of a melting point of 1 70 ° C or higher , and a separation and recovery step of the vinyl-cis-polybutadiene rubber generated from the resulting polymerization mixture, including the one-step method for adding a polymer substance with at least one unsaturated double bond per repeat unit to the system of production of vinyl-cis-polybutadiene rubber. 15. The production method of the vinyl-cis-polybutadiene gel as described in Table 14 above, wherein the polymer substance is at least one selected from polyisoprene, one point crystallizable polybutadiene. of melting from 0 ° C to 150 ° C, polybutadiene and liquid thereof and derivatives thereof. 16. The vinyl-cis-polybutadiene rubber production method as described in item 14 or 1 above, wherein the amount of polymer substance to be added to the production system is within a range of 0.01% to 50% by mass of the vinyl-cis-polybutadiene rubber to be obtained. 7. The method of producing vinyl-cis-polybutadiene rubber as described in any of points 14 to 16 above, wherein the step of adding the polymer substance to the system of prod It is carried out in the polymerization mixture at a suitable time point of the cis-1,4 polymerization step to the separation and recovery step of the vinyl-cis-polybutadiene gel generated from the polymerization mixture obtained after finish the polymerization 1, 2. 8. The production method of vinyl-cis-polybutadiene rubber as described in any of points 14 to 17 above, wherein the hydrocarbon series solvent is a hydrocarbon series solvent with a solubility parameter of 9.0 or less. 9. A butadiene rubber composition prepared by compounding the vinyl-cis-polybutadiene rubber obtained by the production method described in any of the points from 14 to 18 above, in a proportion of 1 to 300 parts by weight. mass per 1000 parts by mass of a rubber selected from a natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber or a mixture of at least two types thereof. 20. A butadiene rubber composition for a rim, wherein the vinyl cis-polybutadiene rubber obtained by the production method described in any of the above 14 to 18 points and / or the butadiene rubber composition. described in points 12, 1 3 or 1 9 above is used.

In a preferred embodiment, the vinyl cis-polybutadiene rubber of the present invention (hereinafter abbreviated as "VCR") is a novel VCR wherein 1,2-polybutadiene is 1,2-polybutadiene of a melting point. of 170 ° C or greater, wherein the polymer substance is of a lower melting point than that of 1,2-polybutadiene with at least one unsaturated double bond per repeating unit (sometimes abbreviated hereafter as "substance of unsaturated polymer ") is at least one selected from polyisoprene, crystallizable polybutadiene with a melting point below 170 ° C, liquid polybutadiene and derivatives thereof, and wherein the 1,2-polybutadiene is from a melting point of 170 ° C or greater and the unsaturated polymer substance is concurrently present in the rubber matrix of the cis-polybutadiene and are dispersed therein. Due to the concurrent presence of the 1, 2-polybutadiene of high melting point it exerts a very strong interaction between the polymers as an excellent reinforcing component and said unsaturated polymer substance with a relatively low melting point, such as polyisoprene, consecutively , the VCR according to the present invention has a markedly improved dispersibility of the high melting point 1,2-polybutadiene in the cis-polybutadiene rubber as a component of the matrix due to the compatible effect of the unsaturated polymer substance present concurrently , compared to the VCR of the related technique, so that the content of high-melting 1,2-polybutadiene as an excellent reinforcing component can be high. The characteristics of the VCR according to the present invention as described above make possible a large improvement of different physical-chemical properties strongly demanded in the production of tire articles and for other uses. When the VC R of the present invention is used in a butadiene rubber composition for the rim, in particular, the composition has a very small proportion of swelling in the die (as the ratio of the diameter of the composite to the diameter of the tire). side hole during extrusion) during the production of the rim, so that the composition exerts a large processing capacity and extrusion operation. Additionally, the vulcanized product of the composition exerts excellent properties of breaking strength, abrasion resistance, sliding friction resistance and the like, mainly required for the side cords of the rims and the like. Due to the resistance to flexion-rotu ra-growth of the same is very large and the rigidity of it is high, in addition the amount of the reinforcement material such as carbon and silica that are going to be used can be reductive, making possible a low consumption of fuel due to the decrease in the weight of the tire. Therefore, the rim that uses the VCR of the present invention as a raw material for the side ropes and the like exerts an excellent operating stability and high speed durability and additionally makes possible a low fuel consumption. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of a dispersion mode of the unsaturated polymer substance in relation to the 1,2-polybutadiene crystal fiber of a melting point of 170 ° C or higher. Figure 2 is another schematic view of the dispersion mode in the unsaturated polymer substance in relation to the glass fiber of 1,2-polybutadiene of a melting point of 170 ° C or higher. Figure 3 is still another schematic view of a dispersion mode of the unsaturated polymer substance in relation to the 1,2-polybutadiene crystal fiber of a melting point of 170 ° C or higher. Figure 4 is a further schematic view of a dispersion mode of the unsaturated polymer substance in relation to the glass fiber of 1, 2-polybutadiene with a melting point of 170 ° C or higher. Figure 5 is an electron micrograph illustrating the microstructure of the vinyl-cis-polybutadiene rubber obtained in Comparative Example 1. Figure 6 is an electron micrograph illustrating the microstructure of the vinyl-cis-polybutadiene rubber obtained in the Comparative Example 1. Figure 7 is an electron micrograph illustrating the microstructure of the vinyl-cis-polybutadiene rubber obtained in Comparative Example 3. Figure 8 is an electron micrograph illustrating the microstructure of vinyl-cis-rubber polybutadiene obtained in Comparative Example 4. In the figures, the symbol "1" expresses the matrix; "2", the glass fiber of 1,2-polybutadiene having a melting point of 170 ° C or higher; "3", the microparticle of the unsaturated polymer substance. Detailed Description of the Invention The VCR of the present invention generally has the following constitution. Specifically, the VCR generally contains (1) from one to 50 parts by mass of 1,2-polybutadiene of a melting point of 170 ° C or higher; (2) 100 parts by mass of cis-polybutadiene rubber and (3) an unsaturated polymer substance in an amount of 0.01% to 50% by mass of the total of (1) and (2). Additionally, 1,2-polybutadiene of melting point of 170 ° C or greater as component (1) generally forms a glass fiber with the average crl length of the fiber being mono-dispersed along the short axis of the fiber. 0.2 μm or less, and the aspect ratio being 1 0 or less, which is a short fiber shape with an average crl number of mono-dispersed fibers of 10 or more. The glass fiber of 1,2-polybutadiene as component (1) in a short fiber shape of average length of the mono-dispersed fiber crl along the short axis of 0.2 μm or less, preferably 0.1 μm less; with an aspect ratio of 10 or less, preferably 8 or less; the average number of the mono-d ispersed fiber crl being 1 0 or greater, preferably 1 5 or more and additionally a melting point of 170 ° C or higher, preferably from 1 90 ° C to 220 ° C. The cis-polybutadiene rubber as the component (2) preferably has the following characteristics. In other words, the cis-polybutadiene rubber as the component (2) has a Mooney viscosity (ML1 + at a temperature of 1 00 ° C abbreviated hereinafter as "ML"), or preferably from 10 to 50, more Preferably from 10 to 40. In this way, the improved effective operating capacity during the manufacture of compounds, although the dispersion of component (1) in component (2) is improved. Additionally, the cis-polybutadiene horn as component (2) preferably has the following characteristics. In other words, the viscosity thereof in a toluene solution (centipoise / 25 ° C, hereinafter abbreviated as "T-cp") is preferably 10 to 150, more preferably 10 to 100; and [?] (intrinsic rate) is from 1.0 to 5.0, preferably from 1.0 to 4.0. additionally, the content ratio of the 1,4-cis structure is 80% by mass or greater, preferably 90% by mass or greater. Additionally, the cis-polybutadiene rubber as the component (2) substantially never contains gel material. In this description, the phrase "substantially never contains gel material" means that insoluble matters of toluene are 0.5% by mass or less. The end and / or main chain of the polybutadiene rubber obtained by the cis-1,4 polymerization can be modified. As said modifier, the organic silicone compounds containing at least one amino group and an alkoxy group, organic silicone compounds containing an alkoxy group, unsaturated carboxylic acid derived therefrom, halogen series compounds and compounds containing heteroanillos of three members. The amount of said modifier to be used is 0.01 to 150 mmol per 100g of the generated polybutadiene (polybutadiene rubber). When the amount of the modifier to be used is smaller, the effect of modification can hardly be exercised. When the amount of it that is going to be used is too much, the modifier is still not reactive and is likely to remain in the polybutadiene. Laborious work is required to imitate the modifier, in a way that is not preferred. In this description, the Mooney viscosity of the modified product is preferably increased by no or more, compared to the original rubber before the modification. To promote the reaction, organic peroxides can be added. Preferably, the modified polybutadiene obtained by the method has a Mooney viscosity (M L1 +, 1 00 ° C) within a range of 20 to 80 and has an average molecular weight of 200,000 to 1,000,000 by the method of gel permeation, where 80% by mass or more of the repeating units have a structure of cis-1, 4. Additionally, the content of the vinyl structure in the microstructure is preferably 15% by mass or less. In this description, the insoluble materials in toluene express gel materials adhered to a metal network after filtration, dissolving 100 g of the rubber sample and 400 ml of toluene completely in an Erlenmeyer flask in a retention time ( temperature 25 ° C), and filtering the resulting solution, using a filter apparatus adapted with a 200-mesh metal network. The proportion expresses a measured value by vacuum drying the network attached with the gel to measure the amount adhered to calculate the percentage of the rubber in the sample. Additionally, [?] (Intrinsic viscosity) is a value determined according to the following formula, placing 0.1 g of the sample rubber and 100 ml of toluene in an Erlenmeyer flask, completely dissolving the sample rubber at a temperature of 30C, and then placing the 10 ml solution in a Canon Fenske dynamic viscometer in a water bath controlled by a thermostat at a temperature of 30 ° C, and measuring the drop point (T) of the solution. ? sp = T / To - 1 (T0: toluene drop time only)? sp / c = [?] + k '[?] 2C (? sp: specific viscosity; k ': equal to Huggins constant (0.37); C: concentration of the sample (g / ml)) The ratio between the crystal fiber of 1,2-polybutadiene as the component (1) and the cis-polybutadiene as the component (2) is from one to 50 parts by mass , preferably from one to 30 parts by mass of the glass fiber of 1,2-polybutadiene as the component (1) to 100 parts by mass of the cis-polybutadiene as the component (2). Within the range, the following disadvantages can be avoided: when the amount of the 1,2-polybutadiene crystal fiber is so great that it exceeds 50 parts by mass, the short fiber crystal of the glass fiber of 1, 2 - polybutadiene in the cis-polybutadiene cell is likely to be large, causing a small dispersion capacity thereof; when the amount of the glass fiber and 1,2-polybutadiene is small, less than one part by mass, the reinforcing capacity with the short fiber glass is deteriorated. Therefore, problems hardly occur, so that the characteristic elastic modulus, the resistance to bending-breaking-growing and the degradation by oxidation are exerted with difficulty and the processing capacity is impaired. Therefore, this range is preferred. In addition, the proportion of the unsaturated polymer substance as component (3) is from 0.01% to 50% by mass, preferably from 0.01% to 30% by mass of VC R, as described above. The range is preferable because the deterioration of the dispersion capacity due to the addition of the 1,2-polybutadiene crystal fiber as the component (1) and a deterioration associated with different physical-chemical properties can be prioritized. of the VCR can be deleted. In addition, the suppression of 1,2-polybutadiene from a melting point of 1 70 ° C or higher as the component (1) and the unsaturated polymer substance as the component (3) is from 0.02 to 1 00 parts in mass, preferably from 0.05 to 80 parts by mass of component (3) per 100 parts by mass of component (1). Additionally, the total amount of the components (1) and (3) is from 0.01 to 100 parts by mass, preferably from 1.03 to 90 parts by mass per 100 parts by mass of the cis-polybutadiene rubber as the component (2). The production method of the VCR according to the present invention is described in detail below. For the production of the VCR according to the present invention, the 1,3-butadiene is generally polymerized, using a solvent of hydrocarbon series. The hydrocarbon series solvent is preferably a hydrocarbon series solvent with a solubility parameter (hereinafter abbreviated as "SP value") of 9.0 or less and is more preferably a hydrocarbon series solvent with a solubility parameter of 8.4 or less. The hydrocarbon series solvent with a solubility parameter of 9.0 or less includes, for example, aliphatic hydrocarbons and alicyclic hydrocarbons, such as n-hexane (SP value: 7.2), n-pentane (SP value: 7.0), n- octane (SP value: 7.5), cyclohexane (SP value: 8.1) and n-butane (SP value: 6.6). Among them, for example, cyclohexane is preferred. The SP values of these solvents are known in references, such as the "Rubber Industry Manual" (Gomu Kogyo Binran) (4th edition, Nippon Rubber Association Foundation (Nippon Gomu Kyokai), issued on January 20 , 1994, page 721). By using a solvent with an SP value preferably greater than 9.0, the crystal dispersion of the short crystal fiber of the 1,2-polybutadiene in the cis-polybutadiene rubber is in an expected condition according to the invention, so that one can preferably exert an excellent characteristic of die swelling, high tensile stretch, tensile strength and high flex-break-grow performance. First, 1,3-butadiene and the solvent are mixed together to adjust the concentration of water in the resulting solution. The water is within a range of preferably 0.1 to 1.0 mmol, particularly from 0.2 to 1.0 mmol per one mole of an organic aluminum chloride used as the cis-1,4 polymerization catalyst in the solution. The range is preferably because sufficient catalytic activity can be obtained to produce a preferable content of a molecular weight of the cis-1,4 structure, and because the occurrence of gel can be suppressed during the polymerization, to avoid adhesion of the gel in the polymerization tanks or similar, so that the continuous polymerization time can be prolonged. As a method for adjusting the concentration of water, known methods are applicable. A method of addition and dispersion through porous filters is effective (JP-A-4-85304). To the solution obtained by adjusting the water concentration, an organic aluminum chloride is added as one of the cis-1,4 polymerization catalysts. As said organic aluminum chloride, a compound represented by the general formula A1RnX3.n can be preferably used. Specific examples thereof include diethylaluminum monochloride, diethylaluminum monobromide, diisobutylaluminum monochloride, dicyclohexylaluminum monochloride, diphenylaluminum monochloride and diethylaluminum sesquichloride. The amount of said organic aluminum chloride to be used is preferably 0.1 mmol or more, 0.5 to 50 mmol per one mole of the total amount of 1,3-butadiene. Then, a soluble cobalt compound is added as another of the cis-1,4 polymerization catalysts to the mixture solution in which the organic aluminum chloride was preliminarily added, for the cis-1,4 polymerization of 1, 3-libutadiene. Said soluble cobalt compound includes those found in the hydrocarbon series solvents or liquid 1,3-butadiene to be used or dispersed uniformly therein, for example, a β-diketone cobalt complex. , such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, a complex of β-keto cobalt acid ester, such as cobalt acetoacetic acid ester complex, cobalt salts of organic carboxylic acid acids with 6 or more carbon atoms, such as cobalt octoate, cobalt naphthenate and cobalt benzoate and halogenated cobalt complexes, such as pyridine complex and cobalt chloride and ethyl alcohol and cobalt chloride complex. The amount of said soluble cobalt compound to be used preferably is 0.001 mmol or greater, more preferably 0.005 mmol or greater per one mole of 1,3-butadiene. The molar ratio (A1 / Co) of an organic aluminum chloride to said soluble cobalt compound is 10 or greater, particularly 50 or greater. Still further, nickel organic carboxylate salts, organic nickel complex salts, organic lithium compounds, neodymium organic carboxylate salts, and organic neodymium complex salts other than the soluble cobalt compound can also be used. The temperature for the cis-1,4 polymerization is generally within the temperature range above 0 ° C to 100 ° C, preferably 10 ° C to 100 ° C, more preferably 20 ° C to 100 ° C. The polymerization time (average retention time) is preferably in a range of 10 minutes to 2 hours. The cis-1,4 polymerization is preferably done so that the concentration of the polymer after the cis-1,4 polymerization can be from 5% to 26% by mass. As a polymerization tank, a tank or two or more tanks in conjugation are used. The polymerization is carried out while the solution is mixed together under agitation in the polymerization tank (polymerization apparatus). As the polymerization tank for use in the polymerization, a polymerization tank equipped with a stirring unit can be used for a highly viscous solution, for example, the apparatus described in JP-B-40-2645. For the production of VCR according to the present invention, known molecular weight adjusters can be used, for example, non-conjugated dienes, such as cyclooctadiene, aleño and methylalene (1,2-butadiene) or α-olefins, such as ethylene , propylene and butene-1 during cis-1,4 polymerization. As to further suppress gel generation during the polymerization, gelation prevention agents can be used. Additionally, the content of the cis-1,4 structure in the polymerized product is generally 80% by mass or greater, preferably 90% by mass or greater, with an ML of 10 to 50, preferably 10 to 40 and substantially no Content of gel materials.

The 1,3-butadiene is polymerized 1,2 to produce the VCR by the addition of an organic aluminum compound represented by the general formula A1R3 and carbon sulfide, and the soluble cobalt compound, if necessary, as a catalyst of the 1.2 polymerization to the cis-1,4 polymerization mixture obtained in this way. Then, the resulting 1, 3-butadiene can be added to the polymerization mixture. Otherwise, the resulting 1, 3-butadiene may not be added to the polymerization mixture but may be reacted from the non-reactive 1,3-butadiene. The organic aluminum compound represented by the general formula A1R3 preferably includes trimethylaluminum, triethylaluminum, triisobutylaluminum, tri (n-hexyl) aluminum and triphenylaluminum. The organic aluminum compound is present in an amount of 0.1 mmol or greater, particularly 0.5 to 50 mmol or greater, per one mole of 1,3-butadiene. Without specific limitation, carbon disulfide preferably never contains moisture. The concentration of the carbon disulfide is 20 mmol / L or less, particularly preferably 0.01 to 10 mmol / L. As an alternative to carbon disulfide, known compounds of phenyl isothiocyanate and xanthogenic acid can be used. The temperature for polymerization 1.2 is generally within the range of 0 ° C to 100 ° C, preferably 10 ° C to 100 ° C, more preferably 20 ° C to 100 ° C. The production of 1,2-polybutadiene can be elevated during the 1,2-polymerisation by adding from one to 50 parts by mass, preferably from one to 20 parts by mass of 1,3-butadiene per 100 parts by mass of the mixture. cis-1,4 polymerization to the polymerization system for the polymerization 1,2. The polymerization time (average retention time) is preferably within a range of 10 minutes to 2 hours. The polymerization 1.2 is preferably carried out, so that the concentration of the polymer after polymerization 1.2 could be 9% to 29% by mass. As a polymerization tank, one or two or more tanks are used in conjugation. The polymerization is carried out while the polymerization solution is mixed together under stirring in the polymerization tank (polymerization apparatus). As the polymerization tank for use in the polymerization 1,2, a polymerization tank equipped with a stirring unit for a highly viscous solution can be used, for example, the apparatus described in JP-B-40-2645, because to that the viscosity of the polymerization solution is increased during polymerization 1,2, and the polymer is ready to be added. For the production of VCR according to the invention, the process of producing the VCR by means of cis-1,4 polymerization and subsequent 1,2-polymerization as described above, includes an addition step of a polymer substance of a low melting point with at least one unsaturated double bond per one repeat unit for the VCR production system. When the unsaturated polymer substance is added after the production of the VCR, for example, during compounding, the advantages of the present invention can not be obtained. The addition of said unsaturated polymer substance to a production system is preferably done within the polymerization mixture at a suitable time point of the cis-1,4 polymerization to the 1,2-polymerization, and more preferably at the time of polymerization 1,2. The unsaturated polymer substance is preferably at least one compound selected from polyisoprene, crystallizable polybutadiene with a melting point below 170 ° C, liquid polybutadiene, a polymeric compound containing an oxygen linkage and derivatives thereof. The polyisoprene includes, for example, a general synthetic polyisoprene (cis-1,4-polyisoprene in a content of cis structure of 90% by mass or greater, etc.), liquid polyisoprene and trans-polyisoprene. The crystallizable polybutadiene with a melting point below 170 ° C is preferably a crystallizable polybutadiene with a melting point of 0 ° C to 150 ° C, which includes, for example, 1,2-polybutadiene and trans-polybutadiene with low melting points. The liquid polybutadiene includes, for example, polybutadiene with a very low molecular weight and with an intrinsic viscosity of []] = 1 or less. The polymeric compound containing the oxygen bond is preferably a compound of the ether group, epoxy group, carboxyl group, ester group, hydroxyl group and carbonyl group. Specific compounds thereof include, for example, phenol resin, nylon resin, polyurethane, polyethylene glycol, epoxylated polybutadiene, polyester, epoxy styrene / butadiene copolymer, polyaryl ether and ether copolymer only. By adding said polymeric compound containing the oxygen bond to a polymerization system, the affinity of the interface changes between the cis-polybutadiene as the component of the vinyl rubber matrix cis-polybutadiene and the glass fiber of 1,2- polybutadiene, so that the mono-dispersion of the glass fiber of the glass fiber 1, 2-polybutadiene and various properties of the vinyl cis-polybutadiene rubber can be effectively improved. Additionally, derivatives thereof include, for example, isoprene-isobutylene copolymer, isoprene-styrene copolymer, styrene-isoprene-styrene block copolymer, liquid epoxylated polybutadiene, carboxyl-modified liquid polybutadiene and the like, and hydrogenated products of these derivatives. Among the individual unsaturated polymer substances, preferably isoprene, styrene-isoprene-styrene block copolymer and 1,2-polybutadiene with a melting point of 70 ° C to 110 ° C are used. Additionally, the individual unsaturated polymer substances may be used alone or in a mixture of two or more thereof. When unsaturated polymer substances are added as described above, the dispersibility of 1,2-polybutadiene of a melting point of 170 ° C or higher in the rubber of cis-polybutadiene as the component of the matrix, can be Improved prominently, due to the compatible effect of the unsaturated polymer substance in the resulting VCR, so that the characteristics of the resulting VCR are excellent. The amount of unsaturated polymer substance to be added is within a range preferably from 0.01% to 50% by mass, more preferably from 0.01% to 30% by mass of the vinyl cis-polybutadiene rubber obtained. At any point of the addition time, agitation is also carried out for preferably 10 minutes to 3 hours, more preferably 10 minutes to 30 minutes after the addition. In the case of a polymeric compound containing the oxygen bond, in this case mentioned in this description, the amount thereof to be added is within a range preferably of 0.01% to 20% by mass, more preferably of the 0.01% to 10% by mass of the vinyl cis-polybutadiene rubber obtained. The method of addition in that case is without specific limitation. During the cis 1,4 polymerization, or 1,2-polymerization to produce the vinyl cis-polybutadiene rubber, and / or termination of the polymerization of the vinyl cis-polybutadiene rubber, the addition can be done satisfactorily. The addition at the time of polymerization 1.2 is that which is preferred. After the addition, stirring is preferably carried out for a period of 10 minutes to 3 hours. Preferably, the stirring time is 10 minutes to 30 minutes. In addition to the unsaturated polymer substance, an organic compound containing the oxygen bond is preferably added. The organic compound containing the oxygen bond preferably, for example, includes, compounds of the ether group, epoxy group, carboxyl group, ester group, hydroxyl group and carbonyl group, which include, for example, an acid anhydride; aliphatic alcohol, aromatic alcohol, ether-aliphatic, ether-aromatic, unsaturated carboxylic acid carboxylic acid, aliphatic carboxylic acid or carboxylate ester saturated with aromatic carboxylate ester, carboxylate ester to ifatic. The amount thereof which is to be added is within a range of preferably from 0.01% to 20% by mass, more preferably from 0.01% to 10% by mass of the vinyl cis-polybutadiene horn obtained. The addition method in that case has no specific limitation. The addition can be done satisfactorily during cis polymerization 1, 4 or polymerization 1, 2 to produce the vinyl cis polybutadiene rubber and / or at the termination of the polymerization of the vinyl cis polybutadiene rubber. The addition at the time of polymerization 1, 2 is what is preferred. After the addition, stirring is preferably carried out for a period of 10 minutes to 3 hours, preferably the stirring time is 10 minutes to 30 minutes. After the polymerization reaches a previously determined polymerization ratio, known antioxidants are added according to general methods. Typical examples of such antioxidants include 2,6-di-t-butyl-p-cresol from the phenol series (BHT), trinonylphenyl phosphite from the phosphorus series (TNP), 4,6-bis (octylthiomethyl) -o -cresol from the series of sulfur and dilauryl-3,3'-thiodipropionate (TPL). Antioxidants can be used alone or in combination of two or more of them. Antioxidants are added in 2001 to 5 parts by mass per 100 parts by mass of the VCR. Subsequently, a polymerization terminating agent is added to the polymerization system to terminate the polymerization. The method for this addition includes, for example, methods known per se, such as a method of feeding the polymerization mixture after completion of the polymerization to a polymerization termination tank, and charging to the polymerization mixture a large amount of a polar solvent such as alcohol, such as methane and ethanol and water in the polymerization mixture or introducing inorganic acids, such as hydrochloric acid and sulfuric acid, organic acids, such as acetic acid and benzoic acid and chloride gas hydrogen. Then, the generated VCR is separated and recovered, rinsed and dried according to the general methods, to obtain the intended VCR. The VCR of the present invention obtained in this way is generally found in a proportion of individual components, ie the proportion of 1,2-polybutadiene of a melting point of 170 ° C or higher, cis-polybutadiene rubber and the substance of unsaturated polymer described above, wherein 80% of the microstructure mass of the cis-polybutadiene rubber is cis-1,4-polybutadiene, and the remainder thereof is trans-1,4-polybutadiene and vinyl-1, 2-polybutadiene. The cis-polybutadiene and the unsaturated polymer substance are soluble by themselves (ie, under non-reactive conditions) upon boiling the n-hexane and the 1,2-polybutadiene of a melting point of 170 ° C or higher, and the unsaturated polymer substance physically / chemically adsorbed are insoluble by boiling n-hexane (hereinafter abbreviated as "Hl"). 1,2-Polybutadiene of a melting point of 170 ° C or higher generally has a melting point of 170 ° C to 220 ° C, and is a fiber of short fiber glass as described above. Additionally, the ML of the cis-polybutadiene rubber is from 10 to 50, preferably from 20 to 40 as described above.

Additionally, the VCR of the present invention is composed of 1,2-polybutadiene of a melting point of 170 ° C or higher and the unsaturated polymer substance dispersed uniformly in the rubber matrix of cis-polybutadiene. In the VCR of the present invention, generally, 1,2-polybutadiene of a melting point of 170 ° C or higher is dispersed in the glass fiber as described above. Additionally, the unsaturated polymer substance can be dispersed in various ways in association with the glass fiber of 1,2-polybutadiene with a melting point of 170 ° C or higher. As shown schematically in Figure 1, the different embodiments include, for example, a crystal fiber "2" modality of 1,2-polybutadiene of a melting point of 170 ° C or greater and the microparticle "3" of the substance of unsaturated polymer dispersed separately in matrix "1"; In one embodiment, the microparticle "3" of the unsaturated polymer substance is dispersed in a manner that is adhered to the glass fiber "2" of the 1,2-polybutadiene in the matrix "1" as shown schematically in Figure 2.; a modality of the glass fiber "2" of 1,2-polybutadiene is dispersed in a form that is adhered to the microparticle "3" of the polymer substance n unsaturated in the matrix "1" as shown schematically in figure 3; and an embodiment of the dispersion of the glass fiber "2" of 1,2-polybutadiene in a condition thereof includes dispersed in the microparticle "3" of the unsaturated polymer substance in the matrix "1" as shown schematically in figure 4. A combination modality of two or more of the dispersion modalities shown in figures 1 through 4 may be possible. In figures 1 through 4, "1" expresses the matrix; "2", the glass fiber of 1, 2-polybutadiene from a melting point of 170 ° C or higher; and "3", the microparticle of the unsaturated polymer substance. By the method for the production of the VCR of the present invention, 1,3-butadiene and the hydrocarbon series solvent substantially never contain carbon sulphide and are recovered by removing and removing the carbon disulfide from the mother solution of the polymerization mixture containing the non-reactive 1, 3-butadiene, the hydrocarbon series solvent and the remaining carbon disulfide after the separation and recovery of the VCR generated, generally in the distillation, to remove the 1,3-butadiene and the solvent of hydrocarbon series or through the process of adsorption and separation of carbon disulfide or the process of separation of carbon disulfide adducts. Additionally, 1,3-butadiene and the hydrocarbon series solvent substantially never contain carbon sulfide and are recovered by recovering the three components of a stock solution from the polymerization mixture by distillation and separating and removing the carbon disulfide from the distillate by the adsorption and separation or the separation process of the carbon disulfide adducts. The carbon disulfide and the hydrocarbon series solvent recovered in the aforementioned manner are mixed with the freshly-fed 1,3-butadiene for recycling. The average molecular weight of the boiling mass of the n-hexane soluble material in a polystyrene base in the VCR of the present invention, is preferably from 300,000 to 800,000, more preferably from 300,000 to 600,000 and for easy crystallization from the mono-dispersed fiber. The T-CP / ML ratio between the viscosity of the toluene solution (T-CP) of the boiling of the soluble material in n-hexane of the VCR and the Mooney viscosity (ML) is preferably 1 or more, and more preferably from 1 to 4. According to the VCR's production method, the VCR of the present invention can be produced continuously for a long period of time, profitably industrially, in a high efficiency of the catalyst and with a high processing capacity of the catalyst component. It can be profitably industrially at a high rate of conversion, the VCR can be produced continuously, particularly without adding to the inner wall or the stirring blade inside the polymerization tank or a part with a slow stirring. The VCR of the present invention is used only for use as in a rim or is used to be compounded with another synthetic rubber or natural rubber spread with the oil process if necessary and vulcanized with the addition of fillers, such as black carbon, vulcanization agents, vulcanization accelerators and other general compounding agents. Without specific limitation to any element of the rim, the VCR is used for the side wall or the ropes, or the harrow, the bead filler, the inner lining, the caucus, the rim rope covering or the basic rope .

Without specific limitation of the types of tires, the VCR is used for highly rigid tires, vehicle tires, large vehicle tires such as buses or trucks, rubber tires, light truck tires, SUVs (for use). in 4 x 4) tires, motorcycle tires, and radial tires. Additionally, the VCR is used for the uses of the rope for which mechanical properties and resistance to abrasion are demanded, such as sleeves, bands, golf balls, shoe soles, adhesive, rubber anti-vibration, material to sound test, other complex materials of the series of polymers, other different industrial articles and the like. In addition, the VCR can be used as plastic modifiers. Compositions prepared by adding compounding agents to the VCR of the present invention and molding the resulting mixture together have die swelling ratios lower than 20 or less in an index base, compared to the VCR of the art. related (that diminished value represents excellence), and therefore, have a very large extrusion processing capacity. Additionally, the VCR composition (the composite material) according to the present invention, when it is vulcanized, has already improved the hardness and tension stretch. The VC R composition has notably improved tensile stretch by 1 00% and has an increase of about 40 on an index basis compared to the VCR obtained by the methods of the related art (d so increased value represents excellence. ), and the reinforcement effect has improved in an important way. In addition, the VCR composition has significantly improved flexion-break-growth by about 30 on a base of the index (said increased value represents excellence) and exerts a stress-suppressing force by bending. Additionally, the permeability of gases, such as oxygen as a property of thermal resistance demanded for the operation of tires, plants and the like has decreased by about 5 (said diminished value represents excellence) in a base of indexes, compared with the VCR. obtained by the method of the related technique, exerting an effect in the suppression of heat involved in deterioration by oxidation. To exert the different physico-chemical properties, preferably, the 1, 2-polybutadiene crystal fiber dispersed in the VCR is partially dispersed in a mono-dispersed form like a microfine crystal in the cis-polybutadiene rubber matrix (abbreviated hereinafter referred to as "BR"), and concurrently present with a large crystal fiber of 1,2-polybutadiene with an aggregate structure. In other words, the mono-dispersed crystal fiber of 1, 2-polybutadiene in the BR matrix is preferably a short fiber of an average length of the mono-dispersed fiber crystal along the short axis of 0.2 μm. or smaller, an aspect ratio of 10 or less, the average number of the mono-dispersed fiber crystal being 10 or greater and a melting point of 1 70 ° C or greater. In addition to the 1,2-polybutadiene crystal fiber of a melting point of 170 ° C or higher, preferably, the unsaturated polymer substance is dispersed in the BR matrix. The unsaturated polymer substance preferably has high affinity to the 1,2-polybutadiene crystal fiber in the BR matrix and is dispersed therein in a physical and chemical adsorption condition near the glass fiber (dispersion modes). from figures 2 to 4). As described above, the concurrent dispersion of the glass fiber of 1,2-polybutadiene of a melt point of 1 70 ° C or greater and the amount of unsaturated polymer in the BR matrix makes it preferably to be excellent different. properties. Now, the composition of the preparation prepared by making the compound and composing the VCR of the present invention in another synthetic or natural rubber will be described in greater detail. The rubber composition is suitably composed of from 1 to 300 parts, preferably from 50 to 200 parts by mass of the VCR per 100 parts by mass of natural rubber, synthetic rubber or a mixture of rubber in an appropriate proportion thereof. The synthetic rubber preferably includes, for example, polyisoprene rubber and styrene-butadiene copolymer rubber. Additionally, a butadiene rubber composition for tires may preferably be produced, using the VCR and / or butadiene rubber composition compounded with the VCR. The rubber composition of the present invention can be obtained by molding the individual components using a routine Banbury, open roll, biaxial moulder or moulder. The rubber composition of the present invention can be molded with the compositions of the composition for routine use in rubber industries, such as vulcanization agents, vulcanization accelerators, antioxidants, fillers, process oils, zinc oxide and acid Stearic As curing agents, vulcanizing agents, for example, sulfur, organic peroxides, resin vulcanization agents and metal oxides such as magnesium oxide can be used. As vulcanization accelerators, known vulcanization accelerators can be used, for example, aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates and xanthates. Antioxidants include, for example, the amine ketone series, the imidazole series, the amine series, the phenol series, the sulfur series and the phosphorus series. Fillers include, for example, inorganic fillers, such as silicic anhydride, calcium carbonate, magnesium carbonate, talc, iron sulfide, iron oxide, bentonite, zinc oxide, dimamate earth, china clay, clay, alumina, titanium oxide, silica and carbon black, and organic fillers such as regenerated rubber or rubber. As the process oil, any aromatic series, naphthene series or paraffin series can be used. Examples The examples according to the present invention will now be specifically described. Example 1 A solution of 1.6 kg of 1,3-butadiene dissolved in 18 kg of dehydrated cyclohexane was placed in a 30 L stainless steel reaction tank with a stirrer after the inside was replaced with nitrogen gas, inside the which were mixed 4 mmol of cobalt octoate, 84 mmol of diethylaluminum chloride and 70 mmol of 1,5-cyclooctadiene, for stirring at a temperature of 25 ° C for 30 minutes for cis polymerization. The resulting polymer had an ML of 33, and a T-cp of 59 and a microstructure of structure 1.2 of 0.9 mass%, of structure trans-1.4 of 0.9 mass% and structure cis-1, 4 of 98.2% or in mass. After cis polymerization, the unsaturated polymer substance comprising polyisoprene (IR) (ML = 87; cis-1,4 structure in 98% by mass) was added to the resulting polymerization solution at 5% by mass (as the percentage for the resulting rubber of vinyl cis-polybutadiene), for stirring at a temperature of 25%. ° C for one hour. Immediately after, 90 mmol of triethylaluminium and 50 mmol of carbon disulfide were added to the polymerization solution, for stirring at a temperature of 25 ° C for another 60 minutes for polymerization 1.2. After finishing the polymerization, the resulting polymerization solution was added to 18 liters of methanol with a content of 4,6-bis (octylthiomethyl) -o-cresol in 1% by mass, to deposit and precipitate the polymerized material similar to rubber , which was then separated and rinsed with methanol and dried under vacuum at room temperature. The yield of the vinyl cis-polybutadiene rubber obtained in this way was 80%. Subsequently, the vinyl cis-polybutadiene rubber was treated by boiling it in n-hexane, to separate insoluble materials and soluble materials, which were then dried. The polymer as a boiling soluble substance of n-hexane has a ML of 31, a T-cp of 57, and a T-cp / ML ratio of about 1.8, wherein the microstructure was composed of 1.0 mass% of structure of vinyl- 1.2, 0.9% or mass of trans-1,4 structure, and 98.1% by mass of the cis-1,4 structure. Additionally, the average molecular weight of the polystyrene base mass was 42 x 104, with a [?] Of 1.7. The crystal number of mono-dispersed fibers of 0.2 μm or less along the short axis contained in the vinyl cis-polybutadiene rubber was 100 or more per 400 μm2, while the aspect ratio was or less, and the melting point of 202 ° C. The VCR obtained in this way was subjected to physical-chemical evaluation after the VCR rubber was composed as shown below and in the table. 1. Evaluation points and conditions to carry out the evaluation. Molding Method The molding was done according to the following procedures. [Elaboration of the primary compound] Molding apparatus: a Banbury mixer (volume of 1.7 liters) Number of rotations: 77 rpm Initial temperature: 90 ° C Molding procedures: Time 0: VCR / NR load (natural rubber) Time 0: filling of the filler Time 3 minutes: lifting the ram for cleaning (15 seconds) Time 5 minutes: unloading The discharged material was continuously wound with a 10-inch roller for one minute, for three times and then the extrusion of the sheet.

After the compound was cooled for 2 hours or more, the compound was subjected to the preparation of the secondary compound according to the following procedures. [Preparation of the secondary compound] Upon completion of the elaboration of the primary compound, the preparation of the secondary compound was made according to the following procedures. Molding apparatus: 10-inch roller Roller temperature: 40 ° C to 50 ° C Rotation range: 2 mm Molding procedures: (1) Time 0: winding of discharged material and sulfur loading and vulcanization accelerator ( 2) Time 2 minutes: cut (3) Time 3 minutes: extrusion of the sheet after the elimination of the corners and the round pass Vulcanization period time Measuring device: JSR curelastomer type 2F Measuring temperature: 150 ° C Period measuring time: vulcanization time period of t90 x 2 and t90 x 3 Vulcanization conditions Vulcanization device: press vulcanization Vulcanization temperature: 150 ° C [Evaluation of the physical-chemical properties of natural rubber] The microstructure was analyzed by infrared absorption spectrometry. Based on the absorption intensity ratio at 740 cm-1 for the cis, 967 cm-1 for the trans, and 910 cm-1 for the vinyl, and the microstructure was calculated. The Mooney viscosity (ML1 + 4) was measured in accordance with the JIS K6300 standard. The solution viscosity of toluene (Tcp) was measured at a temperature of 25 ° C, dissolving 2.28 g of the polymer in 50 ml of toluene and using a standard solution to calibrate the viscometer (JIS Z8809) as a standard solution, and the Canon Fenske No. 400 viscometer. M100: value of tension stretching when a vulcanized rubber sample exerted an extension ratio of 100% > , measured in accordance with JIS K6301 standard. TB: tensile strength at rupture of a vulcanized rubber sample, measured according to the JIS standard K6301 The melting point of the 1,2-polybutadiene crystal fiber was determined based on the peak point in the endothermic curve with the differential scanning calorimeter (DSC). [Physical-chemical properties of the composite material] Die swelling Measuring device: an apparatus for measuring the processing capacity manufactured by Monsanto (MPT) Shape of the die: circle L / D: 1, 10 (D = 1.5 mm) Measurement temperature: 100 ° C Cutting speed: 100 sec-1 [Physical-chemical properties of the vulcanized product] Rebound elasticity and tensile strength were measured according to the measurement methods defined by the JIS-K- standard 6301 The tand of dynamic visco-elasticity was measured under conditions of a temperature of 70 ° C, a frequency of Hz and dynamic deformation of 2%, using an RSA2 device manufactured by Reometrics Far East LTD. The exothermic property and the PS (permanent deformation) were measured under conditions of a deformation of 0.445 cm (0.175 inches), a load of 24.948 kg (55 pounds), temperature of 100 ° C and 25 minutes in a Goodrich flexometer according to the ASTM D623 standard. The compressed permanent deformation was measured by compression under conditions of a temperature of 70 ° C and 22 hours with an adjustment compression of the tester manufactured by Ueshima Seisakusho Co., Ltd., in accordance with the JIS K6301 or ASTM D395 standard. As the bending-breaking-growing, a number of bending samples were measured until the break of the sample reached a length of 15 mm or greater with a bending machine manufactured by Ueshima Seisakusho Co., Ltd., according to the ASTM D813 standard. The gas permeability was measured according to the measurement method defined by the JIS K7126 standard. The tand of dynamic visco-elasticity was measured under conditions of a temperature of 70 ° C, a frequency of Hz and dynamic deformation of 2%, using an RSA2 device manufactured by Rheometrics Far East LTd. Table 1 EXAMPLE 2 The vinyl cis-polybutadiene rubber was obtained in the same manner as in Example 1, except for the use of unsaturated polymer substances (additives) that were to be added as shown in Table 2. Comparative Examples 1 al 4 The synthesis and the preparation of the compound were made in the same manner as in Example 1, except that there was no addition of the unsaturated polymer substance (additive), or except that the addition of the unsaturated polymer substance was not during the polymerization, but during the elaboration of the compound after the synthesis of the VCR rubber (the amount of unsaturated polymer substance that was to be added was 10% by mass of the VCR). Table 2 shows the data of the natural rubber of the vinyl rubber compositions cis-polybutadiene. In the table, the number of glass of mono-dispersed fibers was the number per 400 μm2 as an index while said crystal with a length of 0.2 μ or less along the short axis was defined as the single-dispersed SPB fiber crystal. . The microstructure of the high-melting SPB in Comparative Example 1 was 98.8% by mass of the vinyl-1,2 structure, 0.6% by mass of the trasn-1,4 structure, 0.6% by mass of the structure cis-1,4, and a ratio (A / B) between (A) and the BR matrix as a soluble matter upon boiling the n-hexane and (B) a high melting SPB as the insoluble matter upon boiling the n-hexane was 88/12. Additionally, in Comparative Example 1, the? Sp / c of the insoluble polymer upon boiling the n-hexane was 1.5. (? sp / c: they express the magnitude of the molecular weight of the glass fiber of 1,2-polybutadiene, measured at a temperature of 135 ° C, and the solvent used was o-dichlorobenzene). In the table, the IR represents IR2200 (polyisoprene manufactured by JSR); 1,2-PB represent RB820 (1,2-polybutadiene manufactured by JSR).

) O I heard Oí Table 2 I heard O Examples 3 to 12 and Comparative Examples 3 to 5 The vinyl cis-polybutadiene rubber was obtained in the following manner as in Example 1, except for the addition of the polymer and solvent substance shown in Table 3. the table, the IR represents IR2200 (polyisoprene manufactured by JSR); PB liquid is Hiker CTBN 1300 x 8 (liquid polybutadiene with molecular weight of 3,500 manufactured by Ube Industries, Ltd.); Epoxylated PB represents Epolead PB3600 (epoxylated polybutadiene with a pascal viscosity of 33 seconds at a temperature of 45 ° C, such as that manufactured by Daicel Chemical Industries, Ltd.); the aryl ether polymer is Maryarim AWS-0851 (viscosity of 400 stokes at a temperature of 100 ° C as manufactured by NOF Corporation).

Table 3 The data of the composite products with vinyl cis-polybutadiene rubber compositions and vulcanized products thereof are shown below. The examples from 8 to 12 and Comparative Examples 4 and 5, in this description, VCR / NR = 100/0, represent that the NR (natural rubber) was not added during the elaboration of the primary compound, to elaborate the compound. The smallest indices of 100 sec-, gas permeability, exothermic property, PS, compressed permanent deformation and tand show better excellence. The highest hardness indices, M100, TB, EB, TR, Ranborn abrasion, flexion-break-growth and rebound elasticity show better excellence.

Table 4 Table 5 Table 6 Table 7 Figures 5 through 8 are electron micrographs that illustrate the microstructures of the vinyl cis-polybutadiene rubber actually obtained. Figure 5 is a micrograph of a Comparative Example 1, wherein the 1,2-polybutadiene of a melting point of 170 ° C or greater is a hair-like crystal to form aggregation in the matrix. Figure 6 is a micrograph of Example 3; Figure 7 is the micrograph of Example 2; and Figure 8 is the micrograph of Example 4, wherein the aggregation formed by the hair-like crystals in the individual figures is small compared to Figure 5, which indicates a better dispersion.

Claims (19)

1. CLAIMS 1. A vinyl cis-polybutadiene rubber containing 1,2-polybutadiene and a polymer substance of a melting point lower than that of 1,2-polybutadiene and with at least one unsaturated double bond per repeat unit, wherein the 1,2-polybutadiene and the polymer substance are dispersed under conditions physically and / or chemically adsorbed to the rubber of cis-polybutadiene, as the matrix component of the vinyl rubber cis-polybutadiene rubber.
2. 2. The vinyl cis-polybutadiene rubber as described in claim 1, characterized in that the 1,2-polybutadiene and the polymer substance are dispersed in short crystal fibers and / or particles in the rubber of cis-polybutadiene as the component of the vinyl rubber matrix cis-polybutadiene.
3. 3. The vinyl cis-polybutadiene rubber as described in claim 1 or 2, wherein the 1,2-polybutadiene is 1,2-polybutadiene of a melting point of 170 ° C or higher and the substance of The polymer is at least one selected from polyisoprene, polybutadiene which can be crystallized from a melting point of 150 ° C or lower, liquid polybutadiene and derivatives thereof.
4. 4. The vinyl cis-polybutadiene rubber as described in any of claims 1 to 3, characterized in that the unsaturated polymer substance is contained within a range of 0.01% to 50% by mass to the total of the glass fiber of 1,2-polybutadiene and the rubber of cis-polybutadiene.
5. 5. The vinyl cis-polybutadiene rubber as described in any of claims 1 to 4, characterized in that the viscosity of the cis-polybutadiene rubber as the matrix component in a toluene solution at a temperature 25 ° C is within a range of 10 to 150.
6. 6. The vinyl cis-polybutadiene rubber as described in any of claims 1 to 5, wherein the [?] of the rubber cis-polybutadiene as the component of the matrix is within a range of 1.0 to 5.0.
7. 7. The vinyl cis-polybutadiene rubber as described in any of claims 1 to 6, wherein the content of the 1,4-cis structure of the cis-polybutadiene rubber as a component of the matrix is finds within a range of 80% in mass or greater.
8. 8. The vinyl cis-polybutadiene rubber as described in any of claims 1 to 7, characterized in that the Mooney viscosity of the cis-polybutadiene rubber as the component of the vinyl rubber matrix cis-polybutadiene is within a range of 10 to 50.
9. 9. The vinyl cis-polybutadiene rubber as described in any one of claims 1 to 8, characterized in that the polymer substance is an insoluble matter upon boiling the n-hexane.
10. 10. The vinyl cis-polybutadiene rubber as described in any of claims 1 to 9, characterized in that the 1,2-polybutadiene is dispersed in short crystal fiber in the rubber of cis-polybutadiene as the component of the vinyl cis-polybutadiene rubber matrix and the polymer substance is dispersed in the particles thereof, and wherein the short crystal fiber of the 1,2-polybutadiene is dispersed in the particle of the polymer substance.
11. 11. The vinyl cis-polybutadiene rubber as described in claim 10, characterized in that the short crystal fiber of the 1,2-polybutadiene is never contained in the particle of the polymer substance, but is also dispersed in the polymer. cis-polybutadiene rubber as the component of the matrix and where the length of the short glass fiber dispersed in the matrix along the main axis is within a range of 0.2 to 1,000 μm, and the length of the fiber Short crystal of 1, 2-polybutadiene dispersed in the particle of the polymer substance along the main axis is within a range of 0.01 to 0.5 μm.
12. 12. A butadiene rubber composition prepared by preparing the compound of a vinyl cis-polybutadiene rubber according to claim 1 or 2, in a proportion of 10 to 300 parts by weight per 100 parts by weight of a rubber selected from natural rubber, polyisoprene rubber, styrene-butadiene polymer rubber, or a rubber mixture of at least two types thereof .
13. 13. A butadiene rubber composition for a rim, wherein the vinyl cis-polybutadiene rubber is used as described in claims 1 to 11, and / or the butadiene rubber composition as described. is described in claim 12.
14. 14. A method for the production of vinyl cis-polybutadiene rubber by a step of a cis-1,4 polymerization of 1,3-butadiene using the cis-1,4 polymerization catalyst in a hydrocarbon series solvent, one step of a 1,2-polymerization of 1,3-butadiene in the concurrent presence of a 1,2-polymerization catalyst in the resulting polymerization mixture to generate the 1,2-polybutadiene from a melting of 170 ° C or greater, and a step of separating and recovering the vinyl cis-polybutadiene rubber generated from the resulting polymerization mixture, the method including an addition step of a polymer substance with at least one unsaturated double bond per unity of repetition to the rubber production system of vinyl cis-polybutadiene.
15. 15. The method for the production of vinyl cis-polybutadiene rubber as described in claim 14, characterized in that the polymer substance is at least one selected from polyisoprene, polybutadiene which can crystallize from a melting point of 0 ° C to 150 ° C, liquid polybutadiene or derivatives thereof.
16. 16. The vinyl cis-polybutadiene rubber production method as described in claim 14 or15, characterized in that the amount of the polymer substance that is to be added to the production system is within a range of 0.01% to 50% by mass of the vinyl cis-polybutadiene rubber to be obtained.
17. 17. The vinyl cis-polybutadiene rubber production method as described in any of claims 14 to 16, characterized in that the step of adding the polymer substance to the production system is carried out in the polymerization mixture at an appropriate point in time from the cis-1,4 polymerization step to the separating and recovering step of the vinyl cis-polybutadiene rubber generated from the polymerization mixture obtained after the polymerization ended 1,2.
18. 18. The method for producing vinyl cis-polybutadiene rubber as described in any of claims 14 to 17, characterized in that the hydrocarbon series solvent is a hydrocarbon series solvent with a solubility parameter of 9.0 or less. 19. A butadiene rubber composition prepared by preparing the vinyl cis-polybutadiene rubber compound obtained by the production method as described in any of claims 14 to 18, in a proportion of 10 to 300 parts by mass per 100 parts by mass of a rubber selected from natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber or a rubber mixture of at least two types thereof. 20. A butadiene rubber composition for a rim, characterized in that the vinyl cis-polybutadiene rubber obtained by a production method as described in any of claims 14 to 18 and / or the composition is used. of butadiene rubber as described in any of claims 12, 13 or
19. 19.