Polybutadiene composite rubber, preparation method thereof, rubber composition and application thereof

Abstract

The invention relates to the technical field of rubber, and discloses polybutadiene composite rubber, a preparation method and application thereof, and a rubber composition. The composite rubber is composed of a polybutadiene chain segment I in which the molar content of a 1, 4-structural unit is not less than 97% and a polybutadiene chain segment II in which the molar content of a 1, 2-structural unit is not less than 80%, the polybutadiene chain segment II is dispersed in a matrix formed by the polybutadiene chain segment I by forming a crystalline phase, and the crystallization melting temperature of the polybutadiene chain segment II is not lower than 195 DEG C; in the polybutadiene composite rubber, based on the total molar weight of butadiene units, the molar content of the butadiene units in the polybutadiene chain segment I is 70.0-99.5%, and the molar content of the butadiene units in the polybutadiene chain segment II is 0.5-30.0%. The composite rubber provided by the invention has excellent raw rubber strength and physical and mechanical properties and dynamic mechanical properties of vulcanized rubber.

Description

Technical Field

[0001] The invention relates to the technical field of rubber, and in particular to a polybutadiene composite rubber and a preparation method thereof, a rubber composition and applications thereof. Background Art

[0002] Polybutadiene is a polymer containing cis-1,4, trans-1,4 and 1,2-butadiene units in the molecular chain. When the cis-1,4 structure content is higher than 95%, polybutadiene is usually called butadiene rubber. Butadiene rubber has excellent wear resistance, flexibility resistance, resilience, low temperature performance, low hysteresis loss and heat generation, and can be used to manufacture tires, golf ball cores, conveyor belts, hoses, soles, golf ball cores, and modified plastic products. However, the raw strength of butadiene rubber is usually relatively low, resulting in low tensile stress, tensile strength, tear strength and modulus of the vulcanized rubber, which makes it difficult to meet the requirements of modern high-performance safety tires or large engineering tires for synthetic rubber materials.

[0003] In order to improve the raw strength and hardness of butadiene rubber and the tensile stress, tensile strength, tear strength and modulus of vulcanized rubber, in the prior art, a crystallizable polymer (such as syndiotactic-1,2 polybutadiene, syndiotactic polystyrene, polyethylene, trans-1,4 polybutadiene) is introduced into the butadiene rubber matrix by a physical blending (mechanical blending or solution blending) method or a crystallizable polymer (such as syndiotactic-1,2 polybutadiene) is introduced by an in-situ polymerization method. Compared with ordinary butadiene rubber with a similar Mooney viscosity, the above method can improve the hardness of the vulcanized rubber (from 60 to 63), 300% tensile stress, tear strength and flex crack growth resistance, but it leads to a decrease in the tensile strength, elongation at break, resilience and wear resistance of the vulcanized rubber, an increase in compression temperature rise and compression permanent deformation, and an increase in rolling resistance, which is not conducive to the manufacture of high-performance safety tires or large engineering tires (see: US20020037967A1, WO02066554A1, EP0336874A1, WO2002066554A1, Journal of Applied Polymer Science, 1996, 62, 2329-2339 and IPO Conf. Series: Materials Science and Engineering, 2019, 526, 012031).

[0004] Moreover, a common problem in physical blending methods is that cis-1,2-polybutadiene, syndiotactic polystyrene, polyethylene or trans-1,4-polybutadiene and other crystalline polymers are difficult to be compatible and effectively dispersed, resulting in uneven mixing. Even at high temperatures, the blending method may lead to polybutadiene degradation, cross-linking and other problems, causing product deterioration.

[0005] On the other hand, the common problem of in-situ polymerization is that the two catalyst systems used in the first and second stages of polymerization are not compatible, and the second catalyst is used in large quantities. For example, a cobalt-based, nickel-based or neodymium-based catalyst is usually used as the first catalyst for cis-1,4 coordination polymerization of butadiene to prepare high cis polybutadiene, and then a cobalt-based, iron-based or chromium-based catalyst is added as the second catalyst for 1,2-addition coordination polymerization of butadiene to prepare 1,2-syndiotactic polybutadiene. Even for catalysts with the same main metal, the two catalytic active centers have a great influence on each other.

[0006] WO2015084922A1 discloses a method for preparing a blend of cis-1,4 polybutadiene and syndiotactic-1,2 polybutadiene by a butadiene bulk polymerization method. The molar amount of the second cobalt-based catalyst (cobalt 2-ethylhexanoate, an organic aluminum compound and carbon disulfide) used in the method is 1 to 10 times or even 2 to 100 times the molar amount of the first neodymium-based catalyst (a compound containing a lanthanide element, an alkylating agent (composed of aluminoxane, trialkylaluminum, dialkylaluminum hydride and alkylaluminum) and a bromine-containing compound or an iodine-containing compound) to obtain a cis-1,4 polybutadiene / 1,2-polybutadiene complex having a syndiotactic-1,2 polybutadiene content of not more than 5%.

[0007] Moreover, after analysis, in the method disclosed in WO2015084922A1, the amount of alkyl aluminum in the first neodymium catalyst is high, about 131 times the molar amount of the neodymium catalyst, and alkyl aluminum is usually required to be added to the second cobalt catalyst to increase the yield of syndiotactic-1,2 polybutadiene and its content in cis-1,4 polybutadiene / 1,2-polybutadiene complex. Moreover, in order to increase the cis structure content of the butadiene rubber prepared in the first step, it is necessary to polymerize butadiene at a relatively low temperature (such as 32°C), resulting in high viscosity of the polymerization system, low production efficiency, difficult transportation of the rubber solution, and high energy consumption (see: WO2015084922A1, US6291591B1, CN101735402A, CN105814132A, US20100152389A1 and CN100540596C).

[0008] In order to improve the dispersibility of syndiotactic 1,2-polybutadiene in a butadiene rubber matrix, US20100152389A1 and CN100540596C disclose a vinyl cis-polybutadiene rubber and a butadiene rubber composition using the same, wherein the vinyl cis-polybutadiene rubber contains 1,2-polybutadiene and a polymer substance having a melting point lower than that of 1,2-polybutadiene and containing at least one unsaturated double bond in each repeating unit, wherein the polymer substance having a melting point lower than that of 1,2-polybutadiene and containing at least one unsaturated double bond in each repeating unit is at least one unsaturated polymer selected from polyisoprene, a crystallizable polybutadiene having a melting point lower than 170°C, a liquid polybutadiene and a polymer compound containing an oxygen bond, wherein the 1,2-polybutadiene and the polymer substance are dispersed in the cis-polybutadiene rubber as a matrix component of the vinyl cis-polybutadiene rubber in a state of physical, chemical or physicochemical adsorption.

[0009] However, in the above scheme, the high melting point 1,2-polybutadiene and the polymer substance are dispersed in the cis-polybutadiene rubber in the form of short crystal fibers, particles, or both short crystal fibers and particles. The purpose of introducing the polymer substance is to improve the dispersibility of the high melting point 1,2-polybutadiene in the cis-polybutadiene rubber, as well as the processing performance, elastic modulus and flexibility resistance. However, the addition of low molecular weight polyisoprene or polymers containing oxygen bonds such as phenolic resin, nylon resin or polyurethane will also lead to increased heat generation, reduced wear resistance and deterioration of dynamic mechanical properties of the vinyl cis-polybutadiene rubber composite.

[0010] In summary, the methods for preparing polybutadiene rubber in the prior art have the following problems:

[0011] (1) When using the solution in situ polymerization method, two catalyst systems with different properties are required. The two catalyst systems are not compatible. Even for catalysts with the same main metal, the two active centers have a great influence on each other. Moreover, a relatively high yield of syndiotactic 1,2-polybutadiene can only be obtained when the amount of the second catalyst is high and alkyl aluminum needs to be added. In addition, the polymerization reaction needs to be carried out at a relatively low temperature (e.g., 32°C), resulting in high viscosity of the polymerization system, low production efficiency and high energy consumption.

[0012] (2) Vinyl cis-polybutadiene rubber composites prepared in situ by solution or by in situ polymerization can improve the hardness, tensile stress, tear strength and flex crack growth resistance of the vulcanized rubber, but the tensile strength, elongation at break and wear resistance are reduced, the compression temperature rise and compression permanent deformation are increased, and the rolling resistance is increased, which is not conducive to use as high-performance tire tread and sidewall materials.

[0013] (3) In order to improve the dispersibility of syndiotactic 1,2-polybutadiene in cis-polybutadiene rubber, it is necessary to add polyisoprene, crystallizable polybutadiene with a melting point below 170°C, liquid polybutadiene and polymers containing oxygen bonds. However, the addition of low molecular weight polyisoprene or polymers containing oxygen bonds such as phenolic resin, nylon resin or polyurethane will also lead to increased heat generation, reduced wear resistance and deterioration of dynamic mechanical properties of the vinyl cis-polybutadiene rubber.

[0014] Therefore, it is of great significance to develop a polybutadiene composite rubber that can not only improve the modulus, tensile stress, tensile strength, tear strength and flex crack growth resistance of butadiene rubber, but also improve wear resistance and reduce compression temperature rise, compression permanent deformation and rolling resistance, so as to meet the requirements of modern high-performance safety tires or large-scale engineering tires for synthetic rubber materials. Summary of the invention

[0015] The purpose of the present invention is to overcome the above-mentioned defects existing in the prior art and to provide a polybutadiene composite rubber which integrates excellent properties such as Young's modulus, tensile stress at fixed elongation, tensile strength, tear strength, flex crack growth resistance and wear resistance, low compression temperature rise, low compression permanent deformation and low rolling resistance.

[0016] In order to achieve the above-mentioned object, the first aspect of the present invention provides a polybutadiene composite rubber, which is composed of a polybutadiene segment I having a molar content of 1,4-structural units of not less than 97% and a polybutadiene segment II having a molar content of 1,2-structural units of not less than 80%, wherein the polybutadiene segment II is dispersed in a matrix formed by the polybutadiene segment I by forming a crystalline phase, and the crystalline melting temperature of the polybutadiene segment II is not less than 195° C. In the polybutadiene composite rubber, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 70.0-99.5%, and the molar content of butadiene units in the polybutadiene segment II is 0.5-30.0%.

[0017] The second aspect of the present invention provides a method for preparing the polybutadiene composite rubber described in the first aspect, the method comprising: subjecting butadiene monomer to a polymerization reaction in the presence of a catalyst;

[0018] The catalyst contains active components, organic cobalt compounds, organic aluminum compounds, halides and sulfur-containing compounds, and the active components are organic rare earth compounds and / or organic nickel compounds;

[0019] The molar ratio of the active component, the organic cobalt compound, the organic aluminum compound, the halide, the sulfur-containing compound and the butadiene monomer is 1.0×10 -6 -1.0×10 -3:

[0020] 1.0×10 -6 -1.0×10 -3 :1.0×10 -4 -5.0×10 -2 :1.0×10 -5 -2.0×10 -3 :3.0×10 -6 -3.0×10 -3 :1.

[0021] The third aspect of the present invention provides a rubber composition, which contains a filler and the polybutadiene composite rubber described in the first aspect, wherein the filler is selected from at least one of carbon black, silica, calcium silicate, aluminum silicate, calcium carbonate, talc, aluminum hydroxide, aluminum oxide, clay and mica, and the mass content of the polybutadiene composite rubber is 10-90%, preferably 50-85%, based on the total mass of the rubber composition.

[0022] The fourth aspect of the present invention provides the use of the rubber composition of the third aspect in tires, conveyor belts, hoses, shoe soles, golf ball cores, and modified plastic products.

[0023] The technical solution provided by the present invention has the following beneficial effects:

[0024] (1) The polybutadiene composite rubber provided by the present invention contains two polybutadiene segments, wherein the polybutadiene segment II having a molar content of not less than 80% of the 1,2-structural unit is dispersed in a matrix formed by the polybutadiene segment I having a molar content of not less than 97% of the 1,4-structural unit by forming a crystalline phase (the crystalline melting temperature is not less than 195° C.), and has a high degree of dispersion. It can not only improve the raw rubber strength of the polybutadiene rubber, but also improve the hardness, 300% tensile stress, tensile strength, tear strength and flexural resistance of the vulcanized rubber, and can also improve the dynamic mechanical properties, reduce compression heat generation and compression permanent deformation, and improve wear resistance.

[0025] (2) The catalyst system used in the present invention has the characteristics of high catalytic activity and high selectivity for the polymerization of butadiene monomer, avoiding the phenomenon of incompatibility between the two catalyst systems; the content of syndiotactic 1,2-polybutadiene can be flexibly adjusted without adding alkyl aluminum; even if the polymerization reaction is carried out at a relatively high temperature, the polybutadiene segment I can maintain a high cis-1,4 structure content, the polymerization system has a relatively low viscosity, high production efficiency, and low energy consumption. DETAILED DESCRIPTION

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] In the present invention, the molecular weight distribution index refers to the ratio of the weight average molecular weight to the number average molecular weight.

[0028] As mentioned above, the first aspect of the present invention provides a polybutadiene composite rubber, which is composed of a polybutadiene segment I having a molar content of 1,4-structural units of not less than 97% and a polybutadiene segment II having a molar content of 1,2-structural units of not less than 80%, wherein the polybutadiene segment II is dispersed in a matrix formed by the polybutadiene segment I by forming a crystalline phase, and the crystalline melting temperature of the polybutadiene segment II is not less than 195° C. In the polybutadiene composite rubber, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 70.0-99.5%, and the molar content of butadiene units in the polybutadiene segment II is 0.5-30.0%.

[0029] Preferably, the composite rubber is composed of the polybutadiene segment I having a molar content of 1,4-structural units of not less than 98% and the polybutadiene segment II having a molar content of 1,2-structural units of not less than 82%.

[0030] More preferably, the composite rubber is composed of the polybutadiene segment I having a molar content of 1,4-structural units of not less than 98% and the polybutadiene segment II having a molar content of 1,2-structural units of not less than 83%.

[0031] Preferably, in the polybutadiene composite rubber, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 75.0-99.0%, preferably 80.0-98.5%; the molar content of butadiene units in the polybutadiene segment II is 1.0-25.0%, preferably 1.5-20.0%.

[0032] As mentioned above, the second aspect of the present invention provides a method for preparing the polybutadiene composite rubber described in the first aspect, the method comprising: subjecting butadiene monomer to a polymerization reaction in the presence of a catalyst;

[0033] The catalyst contains active components, organic cobalt compounds, organic aluminum compounds, halides and sulfur-containing compounds, and the active components are organic rare earth compounds and / or organic nickel compounds;

[0034] The molar ratio of the active component, the organic cobalt compound, the organic aluminum compound, the halide, the sulfur-containing compound and the butadiene monomer is 1.0×10 -6 -1.0×10 -3 :1.0×10 -6 -1.0×10 -3 :1.0×10 -4 -5.0×10 -2 :1.0×10 -5 -2.0×10 -3 :3.0×10 -6 -3.0×10 -3 :1.

[0035] The present invention directly contacts butadiene monomer with various components in the catalyst, which can effectively avoid the incompatibility of two catalyst systems. In addition, the content of syndiotactic 1,2-polybutadiene can be flexibly adjusted without adding alkyl aluminum. The polymerization reaction can be carried out at a higher reaction temperature, thereby improving the catalytic efficiency and polymerization reaction rate, improving the production efficiency, reducing the viscosity of the polymerization reaction system, and maintaining a very high directional addition selectivity.

[0036] In the present invention, the amount of catalyst used has a great influence on the effect of the polymerization reaction. As the amount of catalyst increases, the polymerization reaction conversion rate increases, and the molecular weight of the polymer decreases; excessive use of catalyst will also increase production costs. Preferably, the molar ratio of the active component, the organic cobalt compound, the organic aluminum compound, the halide, the sulfur-containing compound and the butadiene monomer is 1.0×10 -5 -5.0×10 -4 :3.0×10 -6 -8.0×10 -4 :2.0×10 -4 -1.5×10 -2 :5.0×10 -5 -3.5×10 -3 :5.0×10 -6 -1.0×10 -3 : 1, more preferably 2.0×10 -5 -1.5×10 -4 :5.0×10 -6 -1.0×10 -4 :5.0×10 -4 -5.0×10 -3 :6.0×10 -5 -8.0×10 -4 :7.0×10 -6 -9.0×10-4 :1.

[0037] The present invention has no special requirements for the order of adding the components in the catalyst, as long as it can meet the requirements of the present invention. However, in order to obtain a better catalytic effect, the order of adding the components in the catalyst of the present invention has the following preferred implementations:

[0038] According to a preferred embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the active component, the organoaluminum compound, and the halide, and then sequentially adding the organocobalt compound and the sulfur-containing compound.

[0039] According to another preferred embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the active component and the organic aluminum compound, and then adding the halide, the organic cobalt compound and the sulfur-containing compound in sequence.

[0040] According to another preferred specific embodiment of the present invention, the mixing method of the components in the catalyst and the butadiene includes: first contacting the butadiene with the organic aluminum compound, then adding the active component, then adding the mixture of the halide and the sulfur-containing compound, and finally adding the organic cobalt compound.

[0041] According to another preferred specific embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the organic aluminum compound and the active component, then adding the mixture of the halide and the sulfur-containing compound, and finally adding the organic cobalt compound.

[0042] According to another preferred specific embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the organic aluminum compound, then adding the mixture of the halide and the sulfur-containing compound, and finally adding the active component and the organic cobalt compound in sequence.

[0043] According to another preferred specific embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the organic aluminum compound, then adding the mixture of the halide and the sulfur-containing compound, and finally adding the organic cobalt compound and the active component in sequence.

[0044] According to another preferred embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the halide and the sulfur-containing compound, and then adding the organoaluminum compound, the active component and the organocobalt compound in sequence.

[0045] According to another preferred specific embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the halide and the sulfur-containing compound, and then adding the organoaluminum compound, the organocobalt compound and the active component in sequence.

[0046] According to another preferred embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the halide and the sulfur-containing compound, and then adding the active component, the organoaluminum compound and the organocobalt compound in sequence.

[0047] According to another preferred embodiment of the present invention, the mixing method of each component in the catalyst and the butadiene includes: first contacting the butadiene with the halide and the sulfur-containing compound, and then adding the active component, the organic cobalt compound and the organic aluminum compound in sequence.

[0048] Preferably, the organic rare earth compound is selected from C 6 -C 10 NdClO, C 6 -C 10 Nd and C alkyl carboxylates 6 -C 16 At least one of the organic-substituted neodymium phosphates.

[0049] More preferably, the organic rare earth compound is selected from at least one of neodymium 3-(3-ethylcyclopentyl)propionate, neodymium 3-ethylhexanoate, neodymium 2-ethylheptanoate, neodymium 3-ethylheptanoate, neodymium octanoate, neodymium isooctanoate, neodymium nonanoate, neodymium 2-ethyloctanoate, neodymium 3-ethyloctanoate, neodymium decanoate, neodymium neodecanoate, neodymium cyclohexanoate, neodymium tris[bis(2-ethylhexyl)phosphate] and neodymium tris(2-ethylhexylphosphate)neodymium.

[0050] According to a particularly preferred embodiment of the present invention, the organic rare earth compound is selected from at least one of neodymium 3-ethylhexanoate, neodymium isooctanoate, neodymium 2-ethylheptanoate, neodymium 3-ethylheptanoate, neodymium neodecanoate, neodymium tris[bis(2-ethylhexyl)phosphate] and neodymium tris(2-ethylhexylphosphate).

[0051] According to a particularly preferred embodiment of the present invention, the organic nickel compound is selected from at least one of nickel acetate, nickel benzoate, nickel octanoate, nickel isooctanoate, nickel 2-ethyloctanoate, nickel 3-ethyloctanoate, nickel nonanoate, nickel decanoate, nickel neodecanoate, nickel cyclohexaneate, nickel stearate, nickel acetylacetonate and nickel tetracarbonyl.

[0052] According to a particularly preferred embodiment of the present invention, the organic cobalt compound is selected from at least one of cobalt diacetylacetonate, cobalt triacetylacetonate, cobalt benzoate, cobalt octanoate, cobalt isooctanoate, cobalt decanoate, cobalt neodecanoate, cobalt naphthenate, cobalt stearate, cobalt oleate and cobalt linoleate.

[0053] Preferably, the organoaluminum compound has the general formula AlR 1 R 2 R 3 and / or AlHR 4 R 5 , where R 1 ~R 5 Each independently selected from C 1 -C 6 of alkyl.

[0054] According to a particularly preferred embodiment of the present invention, the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, diethylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, tripentylaluminum and trihexylaluminum.

[0055] Preferably, the halide is selected from the group consisting of a complex of boron trifluoride and an oxygen-containing compound, cumyl chloride, p-dicumyl chloride, 5-tert-butyl-1,3-dicumyl chloride, dichloromethane, dichloroethane, dichloropropane, dichlorobutane, trichloromethane, trichloroethane, trichloropropane, trichlorobutane, trichloropentane, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate. At least one of ester, methyl trichloroacetate, ethyl trichloroacetate, propyl trichloroacetate, butyl trichloroacetate, ethyl trichloropropionate, propyl trichloropropionate, butyl trichloropropionate, ethyl trichlorobutyrate, propyl trichlorobutyrate, butyl trichlorobutyrate, methyl chlorobenzoate, ethyl chlorobenzoate, methyl dichlorobenzoate, ethyl dichlorobenzoate, methyl trichlorobenzoate, ethyl trichlorobenzoate, methyl tetrachlorobenzoate and methyl pentachlorobenzoate.

[0056] According to a particularly preferred embodiment of the present invention, the halide is selected from at least one of a complex of boron trifluoride and an oxygen-containing compound, dichloromethane, dichloroethane, dichloropropane, dichlorobutane, trichloromethane, trichloroethane, trichloropropane, trichlorobutane, trichloropentane, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate and propyl trichloroacetate.

[0057] It should be noted that the present invention has no particular limitation on the method for preparing the complex of boron trifluoride and the oxygen-containing compound, and the method can be carried out by methods known in the art.

[0058] Preferably, the oxygen-containing compound is selected from at least one of alcohols, ethers, ketones and esters.

[0059] According to a particularly preferred embodiment of the present invention, the alcohol is selected from amyl alcohol, tert-amyl alcohol, methyl isobutyl carbinol, hexanol, heptanol, n-octanol, isooctyl alcohol, isononyl alcohol, decanol, phenol, benzyl alcohol, cyclohexanol, docosanol, octacosanol, triacontanol, pentaerythritol, 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 2,3-dimethyl-2,3-butanediol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4- At least one of pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, diethylene glycol, triethylene glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 3-methoxy-1,2-propanediol, 2-hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 1,2,3-heptanetriol and 1,3,5-cyclohexanetriol.

[0060] According to a particularly preferred embodiment of the present invention, the ether is selected from at least one of ethyl ether, methyl propyl ether, ethyl propyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, methyl n-butyl ether, methyl tert-butyl ether, vinyl butyl ether, amyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, anisole, diphenyl ether, tetrahydrofuran and dioxane.

[0061] According to a particularly preferred embodiment of the present invention, the ketone is selected from 3-methyl-2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, dibutyl ketone, methyl isobutyl ketone, 2,4-dimethyl-3-pentanone, 2-octanone, 3-octanone, dibutyl ketone, 2,3-octanedione, ethyl octyl ketone, 2,4-pentanedione, cyclohexanone, cyclopentanone, cycloheptanone, cyclohexanedione, methyl phenyl ketone, butyl phenyl ketone, pentyl phenyl ketone, phenyl tolyl ketone, 3-decanone, 4-decanone, 5-decanone, cyclodecanone, 2-undecanone, 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, At least one of 3-tridecanone, 7-tridecanone, 2-tetradecanone, 3-tetradecanone, 2-pentadecanone, 7-pentadecanone, 8-pentadecanone, 3-hexadecanone, 5-hexadecanone, 6-hexadecanone, 7-hexadecanone, 1-phenyl-1-hexadecanone, 2-heptadecanone, 9-heptadecanone, 2-nonadecanone, 1,2-hexanedione, 3,5-heptanedione, 1,3-phenylpropanedione, cyclopropyl-1,3-butanedione, 3,5,5-trimethyl-1,2-cyclohexanedione, 5,5-dimethyl-cyclohexanedione, 1,1-dimethyl-3,5-cyclohexanedione, 3-butyl-1,4-pentanedione and 2,4-dimethyl-1,3-pentanedione.

[0062] According to a particularly preferred embodiment of the present invention, the ester is selected from at least one of ethyl hexanoate, diethyl oxalate, dibutyl oxalate, methyl methacrylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, phenyl benzoate, dimethyl phthalate, dipropyl phthalate and dioctyl phthalate.

[0063] Preferably, the sulfur-containing compound is selected from carbon disulfide, dimethyl sulfide, methyl ethyl sulfide, diethyl sulfide, methyl propyl sulfide, ethyl n-propyl sulfide, dipropyl sulfide, methyl n-butyl sulfide, ethyl n-butyl sulfide, phenyl isothiocyanate and R 6 -O-CS·SH, and in R 6 -O-CS·SH, R 6 C 1 -C 6 of alkyl.

[0064] More preferably, in R 6 -O-CS·SH, R 6 At least one selected from the group consisting of ethyl, propyl, isopropyl, n-butyl, isobutyl and pentyl.

[0065] It should be noted that, in the method provided by the present invention, when the polymerization reaction temperature is low, the polymerization reaction time can be prolonged; when the polymerization reaction temperature is high, the polymerization time can be effectively shortened.

[0066] Preferably, the conditions of the polymerization reaction include at least: a reaction temperature of -50°C to 120°C, and a reaction time of 0.08h to 30h. More preferably, the conditions of the polymerization reaction include at least: a reaction temperature of -30°C to 110°C, and a reaction time of 0.5h to 30h. Further preferably, the conditions of the polymerization reaction include at least: a reaction temperature of -10°C to 100°C, and a reaction time of 0.5h to 20h.

[0067] According to a particularly preferred embodiment of the present invention, the conditions of the polymerization reaction include at least: a reaction temperature of 30° C. to 70° C. and a reaction time of 1 h to 5 h. The inventors have found that the specific embodiment under this preferred condition can improve the polymerization reaction efficiency and obtain a polymerization product with a suitable molecular weight.

[0068] In the polymerization process of the present invention, all operations are carried out under the protection of inert gas, preferably nitrogen. It should be noted that at the end of the polymerization reaction, water, alcohol or phenolic compounds can be used as terminators to terminate the reaction; carboxylic acids, amine compounds, ester compounds and other auxiliary agents can also be used to terminate the reaction.

[0069] The present invention has no special requirements on the reaction equipment and operation mode of the polymerization reaction, and the polymerization reaction can be carried out using equipment and operation modes known in the art. For example, the polymerization reaction can be carried out in a single polymerization reactor device, in a multi-reactor series device, or in a tubular reactor; with respect to the operation mode of the polymerization reaction, a continuous polymerization or intermittent polymerization operation mode can be adopted, and a bulk polymerization or solution polymerization operation mode can also be adopted; when a solution polymerization method is adopted, a hydrocarbon compound is used as a polymerization solvent, and the concentration of the olefin monomer in the polymerization solvent is 40-200 g / L, preferably 50-180 g / L, and more preferably 60-150 g / L.

[0070] Preferably, the polymerization solvent is selected from pentane, hexane, cyclohexane, heptane, octane, methylcyclopentane, methylcyclohexane and C 6 -C 8 At least one of the isoparaffins is mixed.

[0071] According to a particularly preferred embodiment, the polymerization solvent is at least one selected from pentane, hexane, cyclohexane, heptane, methylcyclohexane and octane.

[0072] As mentioned above, the third aspect of the present invention provides a rubber composition, which contains a filler and the polybutadiene composite rubber described in the first aspect, wherein the filler is selected from at least one of carbon black, silica, calcium silicate, aluminum silicate, calcium carbonate, talc, aluminum hydroxide, aluminum oxide, clay and mica, and the mass content of the polybutadiene composite rubber is 10-90%, preferably 50-85%, based on the total mass of the rubber composition.

[0073] The inventors unexpectedly discovered that by adding the polybutadiene composite rubber provided by the present invention in the aforementioned proportion, a rubber having excellent physical and mechanical properties such as Young's modulus, tensile strength, tensile stress at break and tear strength can be obtained.

[0074] Preferably, the filler is selected from carbon black and / or silicon dioxide, and the carbon black is selected from at least one of furnace black, acetylene black, thermal black, channel black and graphite. The inventors have found that the physical and mechanical properties of the rubber material can be further improved by adopting the specific implementation of this preferred case.

[0075] As mentioned above, the fourth aspect of the present invention provides the use of the rubber composition described in the third aspect in tires, conveyor belts, hoses, shoe soles, golf ball cores, and modified plastic products.

[0076] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise stated, the experimental equipment and raw materials involved are all commercially available products.

[0077] Active ingredient I: neodymium 2-ethylhexanoate;

[0078] Active component II: neodymium neodecanoate;

[0079] Active component III: neodymium tris[bis(2-ethylhexyl)phosphate];

[0080] Active component IV: nickel cyclohexaneate;

[0081] Organic aluminum compound I: a combination of triisobutylaluminum and diisobutylaluminum hydride in a molar ratio of 9:1;

[0082] Organoaluminum compound II: triisobutylaluminum;

[0083] Halide I: a combination of chloroform and ethyl trichloroacetate in a molar ratio of 20:1;

[0084] Halide II: a combination of trichloroethane and ethyl chloroacetate in a molar ratio of 15:1;

[0085] Halide III: complex of boron trifluoride and ether;

[0086] Organocobalt compounds I: cobalt neodecanoate;

[0087] Organic cobalt compounds II: cobalt 2-ethylhexanoate;

[0088] Sulfur compounds I: carbon disulfide;

[0089] Sulfur-containing compound II: a mixture of carbon disulfide and phenyl isothiocyanate in a molar ratio of 20:1;

[0090] In the following examples, the microstructure of the polymer was determined using an infrared spectrometer (FTIR) of Nicolet 6700 from the United States, and the contents of 1,4-structure and 1,2-structure were calculated with reference to the standard SHT 1727-2017 (Infrared spectrometry for determination of microstructure of butadiene rubber);

[0091] Gel permeation chromatography (GPC) was used to characterize the number average molecular weight (M) of the polymers. n ), weight average molecular weight (M w ) and molecular weight distribution index (M w / M n ); the specific test conditions are as follows: Waters 1515 GPC, four chromatographic columns (HT2, HT4, HT5, HT6) were used for testing, the mobile phase was tetrahydrofuran, the elution rate was 1.0 mL / min, the detector temperature was 30°C, and polystyrene standards were used as designated calibration curves to calculate the molecular weight and distribution index.

[0092] Example 1

[0093] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0094] (1) preparing a butadiene-hexane solution with a concentration of 82 g / L;

[0095] (2) At 50° C., 192 mL of the above-mentioned butadiene-hexane solution was contacted with 0.44 mL of the total volume of active component I, organoaluminum compound I and halide I. After 2.0 h of polymerization reaction, 0.26 mL of organocobalt compound I and 0.30 mL of sulfur-containing compound I were added, and the polymerization reaction was continued for 2.0 h. The reaction was terminated with a hexane solution containing 1 wt% of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and ethanol. The rubber was washed with ethanol for 4 times and dried to constant weight to obtain 11.9 g of polybutadiene composite rubber S1 with a yield of 75.6%.

[0096] The molar ratio of the active component I, the organic cobalt compound I, the organic aluminum compound I, the halide I, the sulfur-containing compound I and the butadiene monomer is 7.0×10 -5 :1.4×10-5 :1.2×10 -3 :2.8×10 -4 :1.75×10 -4 :1.

[0097] In the polybutadiene composite rubber S1, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 89.7%, and the molar content of butadiene units in the polybutadiene segment II is 10.3%.

[0098] In the polybutadiene chain segment I, the molar content of 1,4-structure is 98.8%, and the weight average molecular weight (M w ) is 3.49×10 5 g / mol, molecular weight distribution index (M w / M n ) is 2.5.

[0099] In the polybutadiene segment II, the molar content of 1,2-structure is 86.3%, and the crystal melting temperature of the polybutadiene segment II is 198°C.

[0100] Example 2

[0101] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0102] (1) preparing a butadiene-hexane solution with a concentration of 131 g / L;

[0103] (2) At 60° C., 1536 mL of the above-mentioned butadiene-hexane solution was contacted with 5.7 mL of the total volume of active component II, organoaluminum compound I and halide I. After the polymerization reaction for 1.5 h, 4.1 mL of organocobalt compound I and 4.9 mL of sulfur-containing compound I were added, and the polymerization reaction was continued for 2 h. The termination reaction, washing and drying processes in the post-treatment method were the same as those in Example 1, and 167 g of polybutadiene composite rubber S2 was obtained, with a yield of 83.0%.

[0104] The molar ratio of the active component II, the organic cobalt compound I, the organic aluminum compound I, the halide I, the sulfur-containing compound I and the butadiene monomer is 4.6×10 -5 :1.75×10 -5 :9.2×10 -4 :1.8×10 -4 :2.19×10 -4 :1.

[0105] In the polybutadiene composite rubber S2, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 88.0%, and the molar content of butadiene units in the polybutadiene segment II is 12.0%.

[0106] In the polybutadiene segment I, the molar content of 1,4-structure is 99.3%, M w is 3.42×10 5 g / mol,M w / M n is 2.6.

[0107] In the polybutadiene segment II, the molar content of 1,2-structure is 87.3%, and the crystal melting temperature of the polybutadiene segment II is 200°C.

[0108] Example 3

[0109] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0110] (1) preparing a butadiene-hexane solution with a concentration of 131 g / L;

[0111] (2) At 60° C., 1500 mL of the above-mentioned butadiene-hexane solution was contacted with 5.41 mL of the total volume of the active component III and the organoaluminum compound II, and then 0.09 mL of the halide II, 4.8 mL of the organocobalt compound I and 5.8 mL of the sulfur-containing compound II were added. After the polymerization reaction was carried out for 5 hours, the termination reaction, washing and drying processes in the post-treatment method were the same as those in Example 1, and 183.3 g of polybutadiene composite rubber S3 was obtained, with a yield of 93.3%.

[0112] The molar ratio of the active component III, the organic cobalt compound I, the organic aluminum compound II, the halide II, the sulfur-containing compound II and the butadiene monomer is 4.6×10 -5 :2.1×10 -5 :9.2×10 -4 :1.8×10 -4 :2.63×10 -4 :1.

[0113] In the polybutadiene composite rubber S3, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 83.1%, and the molar content of butadiene units in the polybutadiene segment II is 16.9%.

[0114] In the polybutadiene segment I, the 1,4-structure content is 99.5%, M w is 3.37×10 5 g / mol,M w / M n is 3.1.

[0115] In the polybutadiene segment II, the molar content of 1,2-structure is 86.2%, and the crystal melting temperature of the polybutadiene segment II is 198°C.

[0116] Example 4

[0117] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0118] (1) preparing a butadiene-hexane solution with a concentration of 126 g / L;

[0119] (2) At 65° C., 1200 mL of the above-mentioned butadiene-hexane solution was contacted with 4.23 mL of the total volume of active component II and organoaluminum compound I, and then 0.07 mL of halide I was added. After 3.0 h of polymerization reaction, 1.6 mL of organocobalt compound II and 1.9 mL of sulfur-containing compound I were added, and the polymerization reaction was continued for 2.0 h. The post-treatment method was the same as that of Example 1, and 127.9 g of polybutadiene composite rubber S4 was obtained, with a yield of 84.6%.

[0120] The molar ratio of the active component II, the organic cobalt compound II, the organic aluminum compound I, the halide I, the sulfur-containing compound I and the butadiene monomer is 7.5×10 -5 :0.9×10 -5 :1.5×10 -3 :3.2×10 -4 :1.13×10 -4 :1.

[0121] In the polybutadiene composite rubber S4, based on the total molar amount of the composite rubber, the molar content of the polybutadiene segment I is 94.2%, and the molar content of the polybutadiene segment II is 5.8%.

[0122] In the polybutadiene segment I, the molar content of 1,4 structure is 99.0%, M w is 4.92×10 5 g / mol,M w / M n is 3.2.

[0123] In the polybutadiene segment II, the molar content of 1,2 structure is 87.8%, and the crystal melting temperature of the polybutadiene segment II is 201°C.

[0124] Example 5

[0125] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0126] (1) preparing a butadiene-hexane solution with a concentration of 126 g / L;

[0127] (2) At 65° C., 1250 mL of the above-mentioned butadiene-hexane solution was contacted with 4.4 mL of the total volume of active component II, organoaluminum compound I and halide I, and then 1.9 mL of organocobalt compound II and 2.3 mL of sulfur-containing compound II were added. After the polymerization reaction was carried out for 5 h, the termination reaction, washing and drying processes in the post-treatment method were the same as those in Example 1, and 133.9 g of polybutadiene composite rubber S5 was obtained, with a yield of 85.0%.

[0128] The molar ratio of the active component II, the organic cobalt compound II, the organic aluminum compound I, the halide I, the sulfur-containing compound II and the butadiene monomer is 7.5×10 -5 :1.05×10 -5 :1.0×10 -3 :3.2×10 -4 :1.31×10 -4 :1.

[0129] In the polybutadiene composite rubber S5, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment II is 90.7%, and the molar content of butadiene units in the polybutadiene segment II is 9.3%.

[0130] In the polybutadiene segment I, the molar content of 1,4-structure is 99.0%, M w is 4.92×10 5 g / mol,M w / M n is 3.2.

[0131] In the polybutadiene segment II, the molar content of 1,2-structure is 88.5%, and the crystal melting temperature of the polybutadiene segment II is 201°C.

[0132] Example 6

[0133] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0134] A continuous polymerization process was adopted with a butadiene feed rate of 40 L / h and a hexane feed rate of 136 L / h. A total volume of 699 mL of active component II, organoaluminum compound II and halide I were continuously added. After the polymerization reaction for 3.4 h, 789 mL of organocobalt compound I and 954 mL of sulfur-containing compound I were continuously added. The polymerization reaction was continued for 1.1 h. The termination reaction, washing and drying processes in the post-treatment method were the same as those in Example 1, and 66866 g of polybutadiene composite rubber S6 were obtained with a yield of 79.3%.

[0135] The molar ratio of the active component II, the organic cobalt compound I, the organic aluminum compound I, the halide I, the sulfur-containing compound I and the butadiene monomer is 7.0×10 -5 :2.75×10 -5 :1.1×10 -3 :2.8×10 -4 :3.44×10 -4 :1.

[0136] In the polybutadiene composite rubber S6, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 93.1%, and the molar content of butadiene units in the polybutadiene segment II is 7.0%.

[0137] In the polybutadiene segment I, the molar content of 1,4-structure is 99.2%, M w 4.3×10 5 g / mol,M w / M n is 3.2.

[0138] In the polybutadiene segment II, the molar content of 1,2-structure is 87.3%, and the crystal melting temperature of the polybutadiene segment II is 200°C.

[0139] Example 7

[0140] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0141] (1) preparing a butadiene-hexane solution with a concentration of 140 g / L;

[0142] (2) At 65° C., 4 L of the above-mentioned butadiene-hexane solution was contacted with a total volume of 25.2 mL of active component IV and organoaluminum compound II, and 96.2 mL of halide III, and the polymerization reaction was started for 1.5 h. Then, 11.3 mL of organocobalt compound I and 13.7 mL of sulfur-containing compound I were added, and the polymerization reaction was continued for 1.5 h. The termination reaction, washing and drying processes in the post-treatment method were the same as those in Example 1, and 483.3 g of polybutadiene composite rubber S7 was obtained, with a yield of 86.3%.

[0143] The molar ratio of the active component IV, the organic cobalt compound I, the organic aluminum compound II, the halide III, the sulfur-containing compound I and the butadiene monomer is 6.0×10 -5 :1.75×10 -5 :3.6×10 -4 :4.8×10 -4 :2.19×10 -4 :1.

[0144] In the polybutadiene composite rubber S7, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 89.5%, and the molar content of butadiene units in the polybutadiene segment II is 10.5%.

[0145] In the polybutadiene segment I, the molar content of 1,4-structure is 97.9%, M w 2.3×10 5 g / mol,M w / M n is 4.5.

[0146] In the polybutadiene segment II, the molar content of 1,2-structure is 86.5%, and the crystal melting temperature of the polybutadiene segment II is 200°C.

[0147] Example 8

[0148] This embodiment provides a polybutadiene composite rubber and a preparation method thereof. All operations in the preparation process are performed under nitrogen protection. The method comprises:

[0149] (1) preparing a butadiene-hexane solution with a concentration of 126 g / L;

[0150] (2) At 65° C., 1200 mL of the above-mentioned butadiene-hexane solution was contacted with 4.23 mL of the total volume of the organoaluminum compound I and the active component II, and then 0.07 mL of the halide I was added to start the polymerization reaction for 3.0 h. Then, 1.2 mL of the organocobalt compound I and 1.5 mL of the sulfur-containing compound I were added, and the polymerization reaction was continued for 2.0 h. The post-treatment method was the same as that of Example 1, and 121.2 g of polybutadiene composite rubber S8 was obtained with a yield of 80.2%.

[0151] The molar ratio of the active component II, the organic cobalt compound I, the organic aluminum compound I, the halide I, the sulfur-containing compound I and the butadiene monomer is 7.0×10 -5 :7.0×10 -6 :1.4×10 -3 :2.8×10 -4 :8.8×10 -5 :1.

[0152] In the polybutadiene composite rubber S8, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 96.4%, and the molar content of butadiene units in the polybutadiene segment II is 3.6%.

[0153] In the polybutadiene segment I, the molar content of 1,4-structure is 99.0%, M w is 4.92×10 5 g / mol,M w / M n is 3.2.

[0154] In the polybutadiene segment II, the molar content of 1,2-structure is 86.2%, and the crystal melting temperature of the polybutadiene segment II is 201°C.

[0155] Comparative Example 1

[0156] This comparative example is cis-1,4-polybutadiene, and all operations in the preparation process are carried out under nitrogen protection. The method comprises:

[0157] (1) preparing a butadiene-hexane solution with a concentration of 140 g / L;

[0158] (2) At 75° C., 1200 mL of the above-mentioned butadiene-hexane solution was contacted with 7.5 mL of active component IV and organoaluminum compound II, and 69 mL of halide III, and then subjected to polymerization reaction for 3.0 h. The post-treatment method was the same as that of Example 1. 119.8 g of cis-1,4-polybutadiene rubber DS1 was obtained, with a yield of 71.3%.

[0159] The molar ratio of the active component IV, the organoaluminum compound II, the halide III in terms of halogen and the butadiene monomer is 7.0×10 -5 :3.5×10 -4 :5.6×10 -4 :1.

[0160] In the cis-1,4-polybutadiene rubber DS1, the molar content of 1,4-structure is 97.7%, M w 2.85×10 5 g / mol,M w / M n is 4.5.

[0161] Comparative Example 2

[0162] This comparative example is cis-1,4-polybutadiene, and all operations in the preparation process are carried out under nitrogen protection. The method comprises:

[0163] A continuous polymerization process was adopted, with a butadiene feed rate of 40 L / h and a hexane feed rate of 136 L / h. Active component II, organoaluminum compound I and halide I with a total volume of 699 mL were continuously added. After 3.4 hours of polymerization, the termination reaction, washing and drying processes in the post-treatment method were the same as in Example 1, and 62185 g of polybutadiene composite rubber DS2 was obtained with a yield of 73.7%.

[0164] The molar ratio of the active component II, the organoaluminum compound I, the halide I and the butadiene monomer is 7.0×10 -5 :1.1×10 -3 :2.8×10 -4 :1.

[0165] In the cis-1,4-polybutadiene rubber DS2, the molar content of 1,4-structure is 99.2%, M w 4.12×10 5 g / mol,M w / M n is 3.2.

[0166] Test Example 1

[0167] The rubber products prepared in the examples and comparative examples were subjected to performance tests, and the specific test results are shown in Table 1.

[0168] The stress and strain of raw rubber were tested according to Q / SHYS.S05.C11-2008 (tensile stress / strain test of butadiene rubber), and the tensile strength and Young's modulus of raw rubber were tested using an electronic universal material testing machine of Shimadzu AG-ZS model produced by Japan's Shimadzu Corporation.

[0169] A Mooney viscometer model GT-7080-S2 produced by Taiwan High Speed ​​Rail Testing Instrument Co., Ltd. was used to test the Mooney viscosity of raw rubber in accordance with standard GB / T 1232.1-2016. The test temperature was 100°C.

[0170] Table 1

[0171] Example No. Raw rubber tensile strength, MPa Young's modulus, MPa <![CDATA[Mooney viscosity, ML 1+4 100℃ > Example 1 0.40 0.56 50 Example 2 0.42 0.62 56 Example 3 0.43 0.65 68 Example 4 0.17 0.19 42 Example 5 0.22 0.17 46 Example 6 0.18 0.18 53 Example 7 0.21 0.19 50 Example 8 0.17 0.16 45 Comparative Example 1 0.11 0.12 44 Comparative Example 2 0.13 0.13 45

[0172] It can be seen from the results in Table 1 that the raw polybutadiene composite rubber prepared by the method provided by the present invention has improved tensile strength and Young's modulus. In particular, by comparing Example 1 with Comparative Example 1, it can be seen that the raw polybutadiene composite rubber prepared by the method of the present invention has improved tensile strength by 2.64 times and improved Young's modulus by 3.67 times.

[0173] Test Example 2

[0174] The polybutadiene rubber products prepared in the examples and comparative examples were mixed with reference to the basic vulcanization formula required by the national standard GB / T8660-2008 (Evaluation method for solution-polymerized butadiene rubber (BR)), and the performance of the vulcanized rubber was tested after being prepared. The basic vulcanization formula 1 is shown in Table 2, and the specific test results are shown in Table 3.

[0175] Among them, referring to the national standard GB / T528-2009 (Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber), the tensile strength, Young's modulus, tensile stress at break, tear strength and elongation at break of the vulcanized rubber were tested using the INSTRON3300 electronic universal material testing machine produced by Instron Corporation of the United States.

[0176] With reference to the national standard GB / T531.1-2008 (test method for indentation hardness of vulcanized rubber or thermoplastic rubber), the hardness of the vulcanized rubber was measured using a Shore A durometer model GSD-719J-R produced by High Speed ​​Rail Testing Instruments Co., Ltd.

[0177] Table 2: Basic formula for vulcanization 1

[0178]

[0179] Table 3

[0180]

[0181] It can be seen from the results in Table 3 that the Young's modulus, hardness, 300% elongation stress and tensile strength of the vulcanized rubber prepared by the polybutadiene composite rubber prepared by the method provided by the present invention are all improved.

[0182] By comparing Example 1 and Comparative Example 1, it can be seen that the Young's modulus, hardness, 300% tensile stress, tensile strength and elongation at break of the vulcanized polybutadiene composite rubber prepared by the method of the present invention are increased by 18.9%, 8.5%, 3 / 8.8%, 36.6% and 12.4%, respectively.

[0183] Test Example 3

[0184] The polybutadiene rubber products prepared in Example 6 and Comparative Example 2 were mixed with reference to vulcanization formula 2, and the performance of the vulcanized rubber was tested after being prepared. The basic vulcanization formula 2 is shown in Table 4, and the specific test results are shown in Table 5.

[0185] Among them, all performance test methods involved in this test example refer to Test Example 2.

[0186] Table 4: Basic formula for vulcanization 2

[0187]

[0188] Table 5

[0189]

[0190] By comparing Example 6 and Comparative Example 2, it can be seen that the Young's modulus, hardness, 300% tensile stress, tensile strength and tear strength of the polybutadiene rubber vulcanizate prepared by the method of the present invention are increased by 15.6%, 10.0%, 8.1%, 9.8% and 44.6%, respectively.

[0191] Test Example 4

[0192] The polybutadiene rubber products obtained in Example 6 and Comparative Example 2 were mixed according to vulcanization formula 3, and the performance of the vulcanized rubber was tested after being prepared. The vulcanization formula 3 is shown in Table 6, and the specific test results are shown in Table 7.

[0193] Table 6: Vulcanization formula 3

[0194]

[0195] Referring to the national standard GB / T9867-2008 (Determination of the wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrader method)), the volume wear of the vulcanized rubber was measured using a DIN abrasion tester model GT-7012-D produced by High Speed ​​Rail Testing Instrument Co., Ltd. to characterize its wear resistance.

[0196] Referring to the national standard GB / T1681-2009 (determination of the rebound resilience of vulcanized rubber), the rebound resilience tester of the vulcanized rubber sample was carried out using the GT-7042 rebound testing machine of the high-speed rail company.

[0197] Referring to the national standard GB / T1687-1993 (Determination of temperature rise and fatigue resistance of vulcanized rubber in flexure test), the vulcanized rubber samples were tested using a compression heating tester model Y-3000E produced by Beijing Youshen Electronic Instrument Co., Ltd. The test stroke was 4.45mm, the prestress was 1MPa, and the constant temperature chamber was 55°C.

[0198] Referring to the national standard GB / T 13934-2006 (Determination of flex cracking and crack growth of vulcanized rubber or thermoplastic rubber (Demethia type)), the flexural performance test of the vulcanized rubber was carried out using the high-speed rail company model GT-7011-D, and the pre-cut length was 2mm.

[0199] Table 7

[0200]

[0201] By comparing Example 6 and Comparative Example 2, it can be seen that the polybutadiene rubber prepared by the method of the present invention has a 3.0% higher resilience of the vulcanized rubber than cis-polybutadiene; the wear loss is reduced by 2.9%, and the flex crack growth is reduced by 14.1%; the compression heat generation and compression permanent deformation are reduced by 5.9% and 16.7%, respectively.

[0202] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A polybutadiene composite rubber, characterized in that: The composite rubber consists of a polybutadiene segment I with a molar content of 1,4-structural units not less than 97% and a polybutadiene segment II with a molar content of 1,2-structural units not less than 80%. The polybutadiene segment II is dispersed in a matrix formed by the polybutadiene segment I by forming a crystalline phase, and the crystallization melting temperature of the polybutadiene segment II is not less than 195° C. In the polybutadiene composite rubber, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 70.0-99.5%, and the molar content of butadiene units in the polybutadiene segment II is 0.5-30.0%.

2. The polybutadiene composite rubber according to claim 1, wherein The composite rubber is composed of the polybutadiene segment I having a molar content of 1,4-structural units of not less than 98% and the polybutadiene segment II having a molar content of 1,2-structural units of not less than 82%; Preferably, the composite rubber is composed of the polybutadiene segment I having a molar content of 1,4-structural units of not less than 98% and the polybutadiene segment II having a molar content of 1,2-structural units of not less than 83%.

3. The polybutadiene composite rubber according to claim 1 or 2, wherein: In the polybutadiene composite rubber, based on the total molar amount of butadiene units, the molar content of butadiene units in the polybutadiene segment I is 75.0-99.0%, preferably 80.0-98.5%; the molar content of butadiene units in the polybutadiene segment II is 1.0-25.0%, preferably 1.5-20.0%.

4. A method for preparing the polybutadiene composite rubber according to any one of claims 1 to 3, characterized in that: The method comprises: subjecting butadiene monomer to polymerization reaction in the presence of a catalyst; The catalyst contains active components, organic cobalt compounds, organic aluminum compounds, halides and sulfur-containing compounds, and the active components are organic rare earth compounds and / or organic nickel compounds; The molar ratio of the active component, the organic cobalt compound, the organic aluminum compound, the halide, the sulfur-containing compound and the butadiene monomer is 1.0×10 -6 -1.0×10 -3 :1.0×10 -6 -1.0×10 -3 :1.0×10 -4 -5.0×10 -2 :1.0×10 -5 -2.0×10 -3 :3.0×10 -6 -3.0×10 -3 :

1.

5. The method according to claim 4, wherein: The molar ratio of the active component, the organic cobalt compound, the organic aluminum compound, the halide, the sulfur-containing compound and the butadiene monomer is 1.0×10 -5 -5.0×10 -4 :3.0×10 -6 -8.0×10 -4 :2.0×10 -4 -1.5×10 -2 :5.0×10 -5 -3.5×10 -3 :5.0×10 -6 -1.0×10 -3 : 1, preferably 2.0×10 -5 -1.5×10 -4 :5.0×10 -6 -1.0×10 -4 :5.0×10 -4 -5.0×10 -3 :6.0×10 -5 -8.0×10 -4 :7.0×10 -6 -9.0×10 -4 :

1.

6. The method according to claim 4 or 5, wherein: The organic rare earth compound is selected from C6-C 10 Neodymium naphthenate, C6-C 10 Nd2O3 and C6-C 16 At least one of organic-substituted neodymium phosphates; Preferably, the organic rare earth compound is selected from at least one of neodymium 3-(3-ethylcyclopentyl) propionate, neodymium 3-ethylhexanoate, neodymium 2-ethylheptanoate, neodymium 3-ethylheptanoate, neodymium octanoate, neodymium isooctanoate, neodymium nonanoate, neodymium 2-ethyloctanoate, neodymium 3-ethyloctanoate, neodymium decanoate, neodymium neodecanoate, neodymium naphthenate, neodymium tris[bis(2-ethylhexyl)phosphate] and neodymium tris(2-ethylhexylphosphate)neodymium; Preferably, the organic rare earth compound is selected from at least one of neodymium 3-ethylhexanoate, neodymium isooctanoate, neodymium 2-ethylheptanoate, neodymium 3-ethylheptanoate, neodymium neodecanoate, neodymium tris[bis(2-ethylhexyl)phosphate] and neodymium tris(2-ethylhexylphosphate).

7. The method according to any one of claims 4 to 6, wherein: The organic nickel compound is selected from at least one of nickel acetate, nickel benzoate, nickel octanoate, nickel isooctanoate, nickel 2-ethyloctanoate, nickel 3-ethyloctanoate, nickel nonanoate, nickel decanoate, nickel neodecanoate, nickel naphthenate, nickel stearate, nickel acetylacetonate and nickel tetracarbonyl.

8. The method according to any one of claims 4 to 7, wherein: The organic cobalt compound is selected from at least one of cobalt diacetylacetonate, cobalt triacetylacetonate, cobalt benzoate, cobalt octanoate, cobalt isooctanoate, cobalt decanoate, cobalt neodecanoate, cobalt naphthenate, cobalt stearate, cobalt oleate and cobalt linoleate.

9. The method according to any one of claims 4 to 8, wherein: The general formula of the organoaluminum compound is AlR1 R2R3 and / or AlHR4 R5, wherein R1 to R5 are each independently selected from a C1-C6 alkyl group; Preferably, the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, diethylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, tripentylaluminum and trihexylaluminum.

10. The method according to any one of claims 4 to 9, wherein: The halide is selected from the group consisting of a complex of boron trifluoride and an oxygen-containing compound, cumyl chloride, p-dicumyl chloride, 5-tert-butyl-1,3-dicumyl chloride, dichloromethane, dichloroethane, dichloropropane, dichlorobutane, trichloromethane, trichloroethane, trichloropropane, trichlorobutane, trichloropentane, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate, trichloropentane, methyl chloroacetate, ethyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate, trichloroprop ... propyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate, methyl chloroacetate, ethyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate, methyl chloroacetate, ethyl dichloroacetate, propyl dichloroacetate, propyl di At least one of methyl chloroacetate, ethyl trichloroacetate, propyl trichloroacetate, butyl trichloroacetate, ethyl trichloropropionate, propyl trichloropropionate, butyl trichloropropionate, ethyl trichlorobutyrate, propyl trichlorobutyrate, butyl trichlorobutyrate, methyl chlorobenzoate, ethyl chlorobenzoate, methyl dichlorobenzoate, ethyl dichlorobenzoate, methyl trichlorobenzoate, ethyl trichlorobenzoate, methyl tetrachlorobenzoate and methyl pentachlorobenzoate; Preferably, the oxygen-containing compound is selected from at least one of alcohols, ethers, ketones and esters.

11. The method according to any one of claims 4 to 10, wherein: The sulfur-containing compound is selected from at least one of carbon disulfide, dimethyl sulfide, methyl ethyl sulfide, diethyl sulfide, methyl propyl sulfide, ethyl n-propyl sulfide, dipropyl sulfide, methyl n-butyl sulfide, ethyl n-butyl sulfide, phenyl isothiocyanate and R6-O-CS·SH, and in R6-O-CS·SH, R6 is a C1-C6 alkyl group.

12. The method according to any one of claims 4 to 11, wherein: The polymerization reaction conditions include at least: a reaction temperature of -50°C to 120°C, and a reaction time of 0.08h to 30h; Preferably, the polymerization reaction conditions at least include: a reaction temperature of -30°C to 110°C, and a reaction time of 0.5h to 30h.

13. A rubber composition, characterized in that: The rubber composition contains a filler and the polybutadiene composite rubber according to any one of claims 1 to 3, wherein the filler is selected from at least one of carbon black, silicon dioxide, calcium silicate, aluminum silicate, calcium carbonate, talc, aluminum hydroxide, aluminum oxide, clay and mica, and the mass content of the polybutadiene composite rubber is 10-90%, preferably 50-85%, based on the total mass of the rubber composition.

14. Use of the rubber composition according to claim 13 in tires, conveyor belts, hoses, shoe soles, golf ball cores, and modified plastic products.

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