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

Abstract

The present invention relates to the field of rubber technology, and discloses a polybutadiene composite rubber, a preparation method thereof, an application thereof, and a rubber composition. The composite rubber is composed of a polybutadiene segment I having a molar content of not less than 97% of 1,4-structural units and a polybutadiene segment II having a molar content of not less than 80% of 1,2-structural units, 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%. The composite rubber provided by the present invention has excellent green rubber strength and the physical and mechanical properties and dynamic mechanical properties of vulcanized rubber.

Description

Technical Field

[0001] The present invention relates to the field of rubber technology, 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 its molecular chain. Polybutadiene with a cis-1,4 structure content exceeding 95% is commonly referred to as butadiene rubber (BUR). Butadiene rubber exhibits excellent wear resistance, flexibility, resilience, low-temperature performance, low hysteresis loss, and heat generation. It is used in the manufacture of tires, golf ball cores, conveyor belts, hoses, shoe soles, golf ball cores, and modified plastic products. However, the relatively low raw strength of BUR results in low tensile stress, tensile strength, tear strength, and modulus in the vulcanized rubber, making it difficult to meet the synthetic rubber material requirements of modern high-performance safety tires and large-scale engineering tires.

[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 existing technology, a crystallizable polymer (such as syndiotactic-1,2 polybutadiene, syndiotactic polystyrene, polyethylene, trans-1,4 polybutadiene) is introduced into the butadiene rubber matrix through physical blending (mechanical blending or solution blending) or through in situ polymerization. The method introduces a crystallizable polymer (such as syndiotactic-1,2 polybutadiene). Compared with ordinary cis-1,4-butadiene rubber (BR) with a similar Mooney viscosity, the above method can improve the hardness of the vulcanized rubber (from 60 to 63), 300% modulus of elongation, tear strength, and flex crack growth resistance. However, it leads to decreases in the tensile strength, elongation at break, resilience, and wear resistance of the vulcanized rubber, increases in compression temperature rise and compression permanent set, and increases in rolling resistance. This is not conducive to the manufacture of high-performance safety tires or large-scale 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 rubber and crystalline polymers such as syndiotactic-1,2 polybutadiene, syndiotactic polystyrene, polyethylene or trans-1,4 polybutadiene are difficult to be compatible and effectively dispersed, resulting in uneven mixing. Even blending methods at high temperatures can lead to problems such as polybutadiene degradation and cross-linking, causing product deterioration.

[0005] On the other hand, a common problem with in-situ polymerization is that the two catalyst systems used in the first and second stages are incompatible, and the amount of the second catalyst required is high. For example, a cobalt-, nickel-, or neodymium-based catalyst is typically used as the first catalyst for the cis-1,4 coordination polymerization of butadiene to produce high-cis polybutadiene. This is then followed by the addition of a cobalt-, iron-, or chromium-based catalyst as the second catalyst for the 1,2-addition coordination polymerization of butadiene to produce 1,2-syndiotactic polybutadiene. Even for catalysts based on the same primary metal, the two catalytically active sites can significantly influence each other.

[0006] WO2015084922A1 discloses a method for preparing a blend of cis-1,4-polybutadiene and syndiotactic-1,2-polybutadiene using a butadiene bulk polymerization method. In this method, the molar amount of the second cobalt-based catalyst (cobalt 2-ethylhexanoate, an organoaluminum compound, and carbon disulfide) used is 1 to 10 times, or even 2 to 100 times, the molar amount of the first neodymium-based catalyst (a lanthanide-containing compound, an alkylating agent (composed of aluminoxane, trialkylaluminum, dialkylaluminum hydride, and alkylaluminum), and a bromine-containing or iodine-containing compound) to obtain a cis-1,4-polybutadiene / 1,2-polybutadiene composite containing no more than 5% syndiotactic-1,2-polybutadiene.

[0007] Furthermore, analysis reveals that the method disclosed in WO2015084922A1 uses a high amount of aluminum alkyl in the first neodymium catalyst, approximately 131 times the molar amount of the neodymium catalyst. Furthermore, additional aluminum alkyl is often required in the second cobalt catalyst to increase the yield of syndiotactic-1,2-polybutadiene and its content in the cis-1,4-polybutadiene / 1,2-polybutadiene complex. Furthermore, to increase the cis-structure content of the butadiene rubber produced in the first step, butadiene polymerization must be performed at a relatively low temperature (e.g., 32°C). This results in high viscosity in the polymerization system, low production efficiency, difficulty in rubber liquid transportation, 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. 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, which is 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 flexural resistance. However, the addition of low-molecular-weight polyisoprene or polymers containing oxygen bonds such as phenolic resins, nylon resins or polyurethanes 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 incompatible. 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 is 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 a high-performance tire tread and sidewall material.

[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 of the vinyl cis-polybutadiene rubber, reduced wear resistance and deterioration of dynamic mechanical properties.

[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 in the prior art and provide a polybutadiene composite rubber that combines excellent properties such as Young's modulus, tensile stress at modulus, tensile strength, tear strength, flex crack growth resistance and wear resistance, low compression temperature rise, low compression permanent set and low rolling resistance.

[0016] To achieve the above objectives, the present invention provides, in a first aspect, a polybutadiene composite rubber, comprising 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 according to the first aspect, the method comprising: subjecting butadiene monomer to a polymerization reaction in the presence of a catalyst;

[0018] The catalyst contains an active component, an organic cobalt compound, an organic aluminum compound, a halide and a sulfur-containing compound, and the active component is an organic rare earth compound and / or an organic nickel compound;

[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 :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.

[0020] A third aspect of the present invention provides a rubber composition comprising the polybutadiene composite rubber described in the first aspect and a filler, 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.

[0021] 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.

[0022] The technical solution provided by the present invention has the following beneficial effects:

[0023] (1) The polybutadiene composite rubber provided by the present invention contains two polybutadiene segments, wherein the polybutadiene segment II having a molar content of 1,2-structural units of not less than 80% is dispersed in a matrix formed by the polybutadiene segment I having a molar content of 1,4-structural units of not less than 97% by forming a crystalline phase (the crystalline melting temperature is not less than 195°C). The dispersion degree is high, which can not only improve the raw rubber strength of the polybutadiene rubber, but also improve the hardness, 300% modulus of elongation, 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.

[0024] (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 incompatibility of the two catalyst systems; the content of syndiotactic 1,2-polybutadiene can be flexibly adjusted without the need to add alkyl aluminum; even if the polymerization reaction is carried out at a relatively high temperature, the polybutadiene chain 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

[0025] The endpoints of the ranges and any values ​​disclosed herein 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 endpoints of each range, the endpoints of each range and 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 to be specifically disclosed herein.

[0026] In the present invention, the molecular weight distribution index refers to the ratio of weight average molecular weight to number average molecular weight.

[0027] As described 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%.

[0028] 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%.

[0029] 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%.

[0030] 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%.

[0031] 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;

[0032] The catalyst contains an active component, an organic cobalt compound, an organic aluminum compound, a halide and a sulfur-containing compound, and the active component is an organic rare earth compound and / or an organic nickel compound;

[0033] 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.

[0034] The present invention directly brings the butadiene monomer into contact with the components of the catalyst, which can effectively avoid the incompatibility of the two catalyst systems. Furthermore, 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, increasing production efficiency, reducing the viscosity of the polymerization reaction system, and maintaining a high directional addition selectivity.

[0035] In the present invention, the amount of catalyst used has a significant impact on the effect of the polymerization reaction. As the amount of catalyst increases, the polymerization reaction conversion rate increases, but 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.

[0036] 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 better catalytic effect, the order of adding the components in the catalyst of the present invention has the following preferred implementations:

[0037] According to a preferred embodiment of the present invention, the mixing method of the components in the catalyst and the butadiene includes: first contacting the butadiene with the active component, the organoaluminum compound, and the halide, and then adding the organocobalt compound and the sulfur-containing compound in sequence.

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

[0039] According to another preferred embodiment of the present invention, the mixing method of the components in the catalyst and the butadiene includes: first contacting the butadiene with the organoaluminum compound, then adding the active component, then adding the mixture of the halide and the sulfur-containing compound, and finally adding the organocobalt compound.

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

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

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

[0043] According to another preferred embodiment of the present invention, the mixing method of the components 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.

[0044] According to another preferred embodiment of the present invention, the mixing method of the components 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.

[0045] According to another preferred embodiment of the present invention, the mixing method of the components 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.

[0046] According to another preferred embodiment of the present invention, the mixing method of the components 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.

[0047] Preferably, the organic rare earth compound is selected from C6-C 10 Neodymium naphthenate, C6-C 10 Neodymium alkyl carboxylate and C6-C 16 At least one of the organic-substituted neodymium phosphates.

[0048] 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 naphthenate, neodymium tris[bis(2-ethylhexyl)phosphate] and neodymium tris(2-ethylhexylphosphate)neodymium.

[0049] 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]neodymium and neodymium tris(2-ethylhexylphosphate)neodymium.

[0050] 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 octoate, nickel isooctanoate, nickel 2-ethyloctoate, nickel 3-ethyloctoate, nickel nonanoate, nickel decanoate, nickel neodecanoate, nickel naphthenate, nickel stearate, nickel acetylacetonate and nickel tetracarbonyl.

[0051] 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 octoate, cobalt isooctanoate, cobalt decanoate, cobalt neodecanoate, cobalt naphthenate, cobalt stearate, cobalt oleate and cobalt linoleate.

[0052] Preferably, the organoaluminum compound has a general formula of AlR1R2R3 and / or AlHR4R5, wherein R1 to R5 are each independently selected from a C1-C6 alkyl group.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] It should be noted that the present invention has no particular limitation on the preparation method of the complex of boron trifluoride and the oxygen-containing compound, and the preparation method can be carried out using methods known in the art.

[0057] Preferably, the oxygen-containing compound is selected from at least one of alcohols, ethers, ketones and esters.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] Preferably, 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.

[0063] More preferably, in R6-O-CS·SH, R6 is at least one selected from the group consisting of ethyl, propyl, isopropyl, n-butyl, isobutyl and pentyl.

[0064] 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.

[0065] Preferably, the polymerization reaction conditions include at least: a reaction temperature of -50°C to 120°C, and a reaction time of 0.08 h to 30 h. More preferably, the polymerization reaction conditions include at least: a reaction temperature of -30°C to 110°C, and a reaction time of 0.5 h to 30 h. Further preferably, the polymerization reaction conditions include at least: a reaction temperature of -10°C to 100°C, and a reaction time of 0.5 h to 20 h.

[0066] According to a particularly preferred embodiment of the present invention, the polymerization reaction conditions include at least a reaction temperature of 30°C to 70°C and a reaction time of 1 to 5 hours. The inventors have discovered that this preferred embodiment can improve polymerization reaction efficiency and produce a polymer product with a suitable molecular weight.

[0067] During the polymerization reaction of the present invention, all operations are carried out under an inert gas atmosphere, preferably a nitrogen atmosphere. It should be noted that at the end of the polymerization reaction, water, alcohols, or phenolic compounds can be used as terminators to terminate the reaction. Auxiliary agents such as carboxylic acids, amine compounds, and ester compounds can also be used to terminate the reaction.

[0068] The present invention has no special requirements for the reaction equipment and operation mode of the polymerization reaction, and 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 the 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.

[0069] Preferably, the polymerization solvent is selected from at least one of pentane, hexane, cyclohexane, heptane, octane, methylcyclopentane, methylcyclohexane and C6-C8 mixed isoparaffins.

[0070] According to a particularly preferred embodiment, the polymerization solvent is at least one selected from pentane, hexane, cyclohexane, heptane, methylcyclohexane, and octane.

[0071] As described 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.

[0072] The inventors unexpectedly discovered that by adding the polybutadiene composite rubber provided by the present invention in the aforementioned proportions, a rubber having excellent physical and mechanical properties such as Young's modulus, tensile strength, modulus of elongation and tear strength can be obtained.

[0073] Preferably, the filler is selected from carbon black and / or silica, and the carbon black is selected from at least one of furnace black, acetylene black, thermal black, channel black, and graphite. The inventors have discovered that adopting this preferred embodiment can further improve the physical and mechanical properties of the rubber material.

[0074] As mentioned above, 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.

[0075] The present invention will be described in detail below through examples. In the following examples, unless otherwise stated, all experimental instruments and raw materials involved are commercially available.

[0076] Active ingredient I: neodymium 2-ethylhexanoate;

[0077] Active component II: neodymium neodecanoate;

[0078] Active component III: neodymium tris[bis(2-ethylhexyl)phosphate];

[0079] Active component IV: nickel naphthenate;

[0080] Organoaluminum compound I: a combination of triisobutylaluminum and diisobutylaluminum hydride in a molar ratio of 9:1;

[0081] Organoaluminum compound II: triisobutylaluminum;

[0082] Halide I: a combination of chloroform and ethyl trichloroacetate in a molar ratio of 20:1;

[0083] Halide II: a combination of trichloroethane and ethyl chloroacetate in a molar ratio of 15:1;

[0084] Halide III: complex of boron trifluoride and diethyl ether;

[0085] Organocobalt compound I: cobalt neodecanoate;

[0086] Organocobalt compound II: cobalt 2-ethylhexanoate;

[0087] Sulfur compounds I: carbon disulfide;

[0088] Sulfur-containing compound II: a mixture of carbon disulfide and phenyl isothiocyanate in a molar ratio of 20:1;

[0089] In the following examples, the polymer microstructure was determined using a Nicolet 6700 FTIR spectrometer (USA), and the 1,4- and 1,2-structure contents were calculated according to the standard SHT 1727-2017 (Determination of the Microstructure of Butadiene Rubber by Infrared Spectroscopy).

[0090] Gel permeation chromatography (GPC) was used to characterize the number average molecular weight of the polymers. M n ), weight average molecular weight ( M w ) and molecular weight distribution index ( M w / M n ); the specific test conditions are as follows: a Waters 1515 GPC with four chromatographic columns (HT2, HT4, HT5, and HT6) was used for testing. The mobile phase was tetrahydrofuran at an elution rate of 1.0 mL / min, the detector temperature was 30°C, and a polystyrene standard was used as a designated calibration curve to calculate the molecular weight and distribution index.

[0091] Example 1

[0092] 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:

[0093] (1) Prepare a butadiene-hexane solution with a concentration of 82 g / L;

[0094] (2) At 50 °C, 192 mL of the above-mentioned butadiene-hexane solution was contacted with 0.44 mL of the active component I, the organoaluminum compound I, and the halide I. After the polymerization reaction for 2.0 h, 0.26 mL of the organocobalt compound I and 0.30 mL of the 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 mixture was washed with ethanol four times and dried to constant weight to obtain 11.9 g of polybutadiene composite rubber S1 with a yield of 75.6%.

[0095] 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.

[0096] 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 was 89.7%, and the molar content of butadiene units in the polybutadiene segment II was 10.3%.

[0097] In the polybutadiene segment I, the molar content of 1,4-structure is 98.8%, and the weight average molecular weight of the polybutadiene segment I is ( M w ) is 3.49×10 5 g / mol, molecular weight distribution index ( M w / M n ) is 2.5.

[0098] In the polybutadiene segment II, the molar content of 1,2-structure is 86.3%, and the crystalline melting temperature of the polybutadiene segment II is 198°C.

[0099] Example 2

[0100] 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:

[0101] (1) Prepare a butadiene-hexane solution with a concentration of 131 g / L;

[0102] (2) At 60°C, 1536 mL of the above-mentioned butadiene-hexane solution was contacted with 5.7 mL of the active component II, the organoaluminum compound I, and the halide I. After the polymerization reaction for 1.5 h, 4.1 mL of the organocobalt compound I and 4.9 mL of the 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%.

[0103] 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.

[0104] 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 was 88.0%, and the molar content of butadiene units in the polybutadiene segment II was 12.0%.

[0105] In the polybutadiene segment I, the molar content of 1,4-structure is 99.3%, M w 3.42×10 5 g / mol, M w / M n is 2.6.

[0106] In the polybutadiene segment II, the molar content of 1,2-structure is 87.3%, and the crystalline melting temperature of the polybutadiene segment II is 200°C.

[0107] Example 3

[0108] 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:

[0109] (1) Prepare a butadiene-hexane solution with a concentration of 131 g / L;

[0110] (2) At 60°C, 1500 mL of the above-mentioned butadiene-hexane solution was contacted with 5.41 mL 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 h, 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%.

[0111] 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.

[0112] 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 was 83.1%, and the molar content of butadiene units in the polybutadiene segment II was 16.9%.

[0113] In the polybutadiene segment I, the 1,4-structure content is 99.5%, M w 3.37×10 5 g / mol, M w / M n is 3.1.

[0114] In the polybutadiene segment II, the molar content of 1,2-structure is 86.2%, and the crystalline melting temperature of the polybutadiene segment II is 198°C.

[0115] Example 4

[0116] 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:

[0117] (1) Prepare a butadiene-hexane solution with a concentration of 126 g / L;

[0118] (2) At 65°C, 1200 mL of the above-mentioned butadiene-hexane solution was contacted with 4.23 mL of the active component II and the organoaluminum compound I, and then 0.07 mL of the halide I was added. After the polymerization reaction started for 3.0 h, 1.6 mL of the organocobalt compound II and 1.9 mL of the sulfur-containing compound I were added. The polymerization reaction was continued for 2.0 h. The post-treatment method was the same as that in Example 1, and 127.9 g of polybutadiene composite rubber S4 was obtained with a yield of 84.6%.

[0119] 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.

[0120] 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%.

[0121] In the polybutadiene segment I, the molar content of the 1,4 structure is 99.0%, M w 4.92×10 5 g / mol, M w / M n is 3.2.

[0122] In the polybutadiene segment II, the molar content of the 1,2 structure is 87.8%, and the crystalline melting temperature of the polybutadiene segment II is 201°C.

[0123] Example 5

[0124] 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:

[0125] (1) Prepare a butadiene-hexane solution with a concentration of 126 g / L;

[0126] (2) At 65°C, 1250 mL of the above-mentioned butadiene-hexane solution was contacted with 4.4 mL of the active component II, the organoaluminum compound I, and the halide I, and then 1.9 mL of the organocobalt compound II and 2.3 mL of the 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, to obtain 133.9 g of polybutadiene composite rubber S5 with a yield of 85.0%.

[0127] 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.

[0128] 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%.

[0129] In the polybutadiene segment I, the molar content of 1,4-structure is 99.0%, M w 4.92×10 5 g / mol, M w / M n is 3.2.

[0130] In the polybutadiene segment II, the molar content of 1,2-structure is 88.5%, and the crystalline melting temperature of the polybutadiene segment II is 201°C.

[0131] Example 6

[0132] 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:

[0133] 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 in Example 1, to obtain 66,866 g of polybutadiene composite rubber S6 with a yield of 79.3%.

[0134] 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.

[0135] 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 was 93.1%, and the molar content of butadiene units in the polybutadiene segment II was 7.0%.

[0136] 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 / Mn is 3.2.

[0137] In the polybutadiene segment II, the molar content of 1,2-structure is 87.3%, and the crystalline melting temperature of the polybutadiene segment II is 200°C.

[0138] Example 7

[0139] 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:

[0140] (1) Prepare a butadiene-hexane solution with a concentration of 140 g / L;

[0141] (2) At 65°C, 4 L of the above-mentioned butadiene-hexane solution was contacted with 25.2 mL of the active component IV and the organoaluminum compound II, and 96.2 mL of the halide III, and the polymerization reaction was started for 1.5 h. Then, 11.3 mL of the organocobalt compound I and 13.7 mL of the 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%.

[0142] 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.

[0143] 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%.

[0144] 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.

[0145] In the polybutadiene segment II, the molar content of 1,2-structure is 86.5%, and the crystalline melting temperature of the polybutadiene segment II is 200°C.

[0146] Example 8

[0147] 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:

[0148] (1) Prepare a butadiene-hexane solution with a concentration of 126 g / L;

[0149] (2) At 65°C, 1200 mL of the aforementioned butadiene-hexane solution was contacted with 4.23 mL of the organoaluminum compound I and the active component II, and then 0.07 mL of the halide I was added. The polymerization reaction was started 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%.

[0150] 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.

[0151] 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%.

[0152] In the polybutadiene segment I, the molar content of 1,4-structure is 99.0%, M w 4.92×10 5 g / mol, M w / M n is 3.2.

[0153] In the polybutadiene segment II, the molar content of 1,2-structure is 86.2%, and the crystalline melting temperature of the polybutadiene segment II is 201°C.

[0154] Comparative Example 1

[0155] This comparative example is cis-1,4-polybutadiene, and all operations in the preparation process are carried out under nitrogen protection. The method comprises:

[0156] (1) Prepare a butadiene-hexane solution with a concentration of 140 g / L;

[0157] (2) At 75°C, 1200 mL of the aforementioned butadiene-hexane solution was contacted with 7.5 mL of the active component IV and the organoaluminum compound II, and 69 mL of the halide III, and the polymerization reaction was carried out for 3.0 h. The post-treatment method was the same as that in Example 1. 119.8 g of cis-1,4-polybutadiene rubber DS1 was obtained with a yield of 71.3%.

[0158] The molar ratio of the active component IV, the organoaluminum compound II, the halide III calculated as halogen and the butadiene monomer is 7.0×10 -5 :3.5×10 -4 :5.6×10 -4 :1.

[0159] 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.

[0160] Comparative Example 2

[0161] This comparative example is cis-1,4-polybutadiene, and all operations in the preparation process are carried out under nitrogen protection. The method comprises:

[0162] 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 were continuously added with a total volume of 699 mL. After the polymerization reaction for 3.4 h, the termination reaction, washing, and drying processes in the post-treatment method were the same as in Example 1 to obtain 62185 g of polybutadiene composite rubber DS2 with a yield of 73.7%.

[0163] 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.

[0164] 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.

[0165] Test Example 1

[0166] 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.

[0167] The stress and strain of raw rubber were tested in accordance with Q / SHYS.S05.C11-2008 (tensile stress / strain test of butadiene rubber). The tensile strength and Young's modulus of raw rubber were tested using a Shimadzu AG-ZS electronic universal material testing machine from Japan.

[0168] The Mooney viscosity of raw rubber was tested using a GT-7080-S2 Mooney viscometer produced by Taiwan High Speed ​​Rail Testing Instrument Co., Ltd. in accordance with standard GB / T 1232.1-2016 at a test temperature of 100°C.

[0169] Table 1

[0170]

[0171] It can be seen from the results in Table 1 that the tensile strength and Young's modulus of the raw polybutadiene composite rubber prepared by the method provided by the present invention are improved. In particular, by comparing Example 1 and Comparative Example 1, it can be seen that the tensile strength of the raw polybutadiene composite rubber prepared by the method of the present invention is increased by 2.64 times, and the Young's modulus is increased by 3.67 times.

[0172] Test Example 2

[0173] 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)). After the vulcanized rubber was prepared, performance testing was performed. The basic vulcanization formula 1 is shown in Table 2, and the specific test results are shown in Table 3.

[0174] 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, modulus of tensile stress, 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.

[0175] 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 Instrument Co., Ltd.

[0176] Table 2: Basic formula for vulcanization 1

[0177]

[0178] Table 3

[0179]

[0180] It can be seen from the results in Table 3 that the Young's modulus, hardness, 300% modulus modulus 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.

[0181] By comparing Example 1 and Comparative Example 1, it can be seen that the Young's modulus, hardness, 300% modulus 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.

[0182] Test Example 3

[0183] The polybutadiene rubber products prepared in Example 6 and Comparative Example 2 were mixed according 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.

[0184] Among them, all performance test methods involved in this test example refer to Test Example 2.

[0185] Table 4: Basic formula for vulcanization 2

[0186]

[0187] Table 5

[0188]

[0189] By comparing Example 6 and Comparative Example 2, it can be seen that the Young's modulus, hardness, 300% modulus modulus, 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.

[0190] Test Example 4

[0191] The polybutadiene rubber products obtained in Example 6 and Comparative Example 2 were mixed according to vulcanization formula 3, and the vulcanized rubber was prepared and then subjected to performance testing. Vulcanization formula 3 is shown in Table 6, and the specific test results are shown in Table 7.

[0192] Table 6: Curing formula 3

[0193]

[0194] In accordance with the national standard GB / T9867-2008 (Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrader method)), a DIN abrasion tester model GT-7012-D from Gaotie Testing Instrument Co., Ltd. was used to measure the volume wear of the vulcanized rubber to characterize its wear resistance.

[0195] Referring to the national standard GB / T1681-2009 (Determination of the rebound elasticity of vulcanized rubber), the rebound elasticity test of the vulcanized rubber samples was carried out using a rebound testing machine model GT-7042 of the High Speed ​​Rail Company.

[0196] With reference to the national standard GB / T1687-1993 (Determination of temperature rise and fatigue resistance of vulcanized rubber in flexure test), the vulcanized rubber specimens were tested using a compression heating tester model Y-3000E produced by Beijing Youshen Electronic Instrument Co., Ltd. The test stroke was 4.45 mm, the prestress was 1 MPa, and the constant temperature chamber was 55°C.

[0197] With reference to the national standard GB / T 13934-2006 (Determination of flexural cracking and crack growth of vulcanized rubber or thermoplastic rubber (Demessia type)), the flexural performance test of the vulcanized rubber was carried out using the high-speed rail company model GT-7011-D, with a pre-cut length of 2 mm.

[0198] Table 7

[0199]

[0200] 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 vulcanized rubber resilience improved by 3.0% compared with cis-polybutadiene; the wear loss is reduced by 2.9%, the flex crack growth is reduced by 14.1%; the compression heat generation and the compression permanent deformation are reduced by 5.9% and 16.7%, respectively.

[0201] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A polybutadiene composite rubber, characterized in that: The composite rubber 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%. 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%.

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%.

3. The polybutadiene composite rubber according to claim 2, 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 83%.

4. 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%; the molar content of butadiene units in the polybutadiene segment II is 1.0-25.0%.

5. The polybutadiene composite rubber according to claim 4, 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 80.0-98.5%.

6. The polybutadiene composite rubber according to claim 4, 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 II is 1.5-20.0%.

7. A method for preparing the polybutadiene composite rubber according to any one of claims 1 to 6, characterized in that: The method comprises: subjecting butadiene monomer to polymerization reaction in the presence of a catalyst; The catalyst contains an active component, an organic cobalt compound, an organic aluminum compound, a halide and a sulfur-containing compound, and the active component is an organic rare earth compound and / or an organic nickel compound; 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.

8. The method according to claim 7, 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 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.

9. The method according to claim 7 or 8, wherein The organic rare earth compound is selected from C6-C 10 Neodymium naphthenate, C6-C 10 Neodymium alkyl carboxylate and C6-C 16 At least one of the organic-substituted neodymium phosphates.

10. The method according to claim 9, wherein: 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.

11. The method according to claim 10, wherein: 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)neodymium.

12. The method according to claim 7 or 8, 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.

13. The method according to claim 7 or 8, wherein: The organic cobalt compound is selected from at least one of cobalt diacetylacetonate, cobalt triacetylacetonate, cobalt benzoate, cobalt octoate, cobalt isooctanoate, cobalt decanoate, cobalt neodecanoate, cobalt naphthenate, cobalt stearate, cobalt oleate and cobalt linoleate.

14. The method according to claim 7 or 8, wherein The organoaluminum compound has a general formula of AlR1 R2 R3 and / or AlHR4 R5, wherein R1 to R5 are each independently selected from a C1-C6 alkyl group.

15. The method according to claim 14, wherein The organoaluminum compound is at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, diethylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, tripentylaluminum and trihexylaluminum.

16. The method according to claim 7 or 8, 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 ... propyl dichloroacetate, butyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, butyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, propyl dichloroacetate, 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.

17. The method according to claim 16, wherein The oxygen-containing compound is selected from at least one of alcohols, ethers, ketones and esters.

18. The method according to claim 7 or 8, 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.

19. The method according to claim 7 or 8, wherein The polymerization reaction conditions at least include: a reaction temperature of -50°C to 120°C, and a reaction time of 0.08 h to 30 h.

20. The method according to claim 19, wherein The polymerization reaction conditions at least include: a reaction temperature of -30°C to 110°C, and a reaction time of 0.5 h to 30 h.

21. 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 6, 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% based on the total mass of the rubber composition.

22. The rubber composition according to claim 21, wherein Based on the total mass of the rubber composition, the mass content of the polybutadiene composite rubber is 50-85%.

23. Use of the rubber composition according to claim 21 or 22 in tires, conveyor belts, hoses, shoe soles, golf ball cores, and modified plastic products.

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