Copolymers, methods for preparing same, vulcanized rubbers and their uses

Abstract

This invention relates to the field of butadiene rubber and discloses a copolymer, a method for preparing the copolymer, and a vulcanized rubber and its use. The copolymer contains polyethylene segments and butadiene rubber segments, and the weight ratio of the polyethylene segments to the butadiene rubber segments is 0.1:99.9 to 80:20 based on the total amount of the copolymer. The butadiene rubber segments have a cis-1,4-structure content of 90 to 98.5 mol% based on the total amount of the butadiene rubber segments. The length of consecutive methylene sequences in the copolymer is at least 165. The copolymer is synthesized by in-situ polymerization. The polyethylene butadiene rubber block copolymer acts as a solubilizer, promoting the dissolution of the reinforcing polyethylene phase and the butadiene rubber matrix. This allows for the production of a copolymer with good reinforcing filler dispersion without the need for subsequent compounding, thereby solving problems such as phase separation and interfacial failure that exist in blends.

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of Chinese Patent Application No. 202211302115.7, filed on October 24, 2022, the contents of which are incorporated herein by reference.

[0002] [Technical Field] The present invention relates to the field of copolymers, and in particular to copolymers and methods for their preparation, as well as vulcanized rubbers and their uses.

[0003] [Background technology] Butadiene rubber is a type of rubber material that is simply synthesized using inexpensive butadiene monomer. Its molecular chains are regular, contain no other substituents, contain C-C single bonds, and have numerous free chains, making it very soft. Its unique elasticity, excellent abrasion resistance, cold resistance, and dynamic properties have made it indispensable in many fields, including tires, shoemaking, damping and shock absorption, and sealing. However, butadiene rubber also suffers from drawbacks such as low tensile strength, tear strength, and flexural strength, poor anti-slip properties, a tendency to viscous flow at low temperatures, and poor aging resistance, which limit its range of applications. Therefore, to overcome these drawbacks and expand the scope of butadiene rubber's applications, it is necessary to reinforce and modify it.

[0004] US 4,340,685 discloses a cobalt and carbon disulfide catalyst system for the in-situ synthesis of cis-1,4-polybutadiene / syndiotactic 1,2-polybutadiene blends and the production of VCR rubber. The acid gases produced by the use of carbon disulfide are highly corrosive to production equipment and, if left in the rubber, can have a detrimental effect on its properties.

[0005] CN105814132A discloses a method for synthesizing polybutadiene composites by in-situ blending of cis-1,4-polybutadiene and syndiotactic 1,2-polybutadiene. However, the problem is that the in-situ copolymerization method requires the use of two catalyst systems during the polymerization process. In the first step, a lanthanide catalyst is used to polymerize cis-1,4-polybutadiene, and then a cobalt-based catalyst and carbon disulfide are used to polymerize the cis-1,4-polybutadiene mixture to form syndiotactic 1,2-polybutadiene, resulting in the composite polybutadiene.

[0006] US9985115B2, US6291591B2, and US6331594B2 disclose the polymerization of butadiene in saturated alkanes of butadiene rubber using iron, chromium, or molybdenum catalysts to synthesize blends of cis-1,4-polybutadiene / syndiotactic 1,2-polybutadiene.

[0007] The in-situ generated syndiotactic 1,2-polybutadiene is blended with a butadiene rubber solution. However, because the butadiene rubber is dispersible, the polymerization activity is insufficient, making it difficult to control the polymerization process and adjust the composition. More importantly, the two are incompatible, which can easily lead to phase separation and interfacial problems, affecting the material properties.

[0008] At present, it is necessary to develop a new butadiene rubber reinforcing technology to improve the tensile strength and tear resistance of butadiene rubber products, thereby improving the usage properties of butadiene rubber products and extending their service life.

[0009] Summary of the Invention [Problem to be solved by the invention] The present invention aims to improve the tensile strength and tear resistance of existing butadiene rubber materials, and to provide a copolymer and a method for producing the copolymer, as well as a vulcanized rubber and its use. The modification of butadiene rubber is achieved by introducing ethylene structural segments into the butadiene structural segments of butadiene rubber to form a block copolymer.

[0010] [Means for solving the problem] A first aspect of the present invention provides a copolymer, the copolymer being a block copolymer and comprising a polyethylene segment and a butadiene rubber segment, wherein a weight ratio of the polyethylene segment to the butadiene rubber segment, based on the total amount of the copolymer, is 0.1:99.9 to 80:20, and the butadiene rubber segment has a cis 1,4-structure content of 90 to 98.5 mol%, a trans 1,4-structure content of 0.9 to 5.7 mol%, and a 1,2-structure content of 0.6 to 4.3 mol%, based on the total amount of the butadiene rubber segment, and the length of consecutive methylene sequences in the copolymer is at least 165.

[0011] A second aspect of the present invention provides a method for preparing a copolymer, the method comprising: Step (1) is a step of polymerizing ethylene in the presence of an organic solvent, a catalyst, and an aluminum-containing cocatalyst-1 to obtain a polyethylene product, wherein the polymerization temperature is 20 to 70°C, the ethylene pressure is maintained at 1 to 70 bar, and the polymerization time is 1 to 80 minutes; (2) introducing 1,3-butadiene monomer into the polyethylene product and removing unreacted ethylene monomer; and step (3) adding a chloroaluminum-containing cocatalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between 1,3-butadiene monomer and the polyethylene active segments in the polyethylene product, thereby obtaining the copolymer; The catalyst is at least one selected from the compounds represented by formula 1, formula 2, and formula 3.

[0012] [ka]

[0013] (wherein X is chlorine or bromine, R1 is a substituent mono-substituted at the 2- or 4-position on the benzene ring, or identical or different substituents di-substituted at the 2-, 4-, or 2-, 6-positions on the benzene ring, or identical or different substituents tri-substituted at the 2-, 4-, and 6-positions on the benzene ring, wherein the substituents are -F, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH6H5, or -CH(CH6H5)2; R3 is -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH6H5, or -CH(CH6H5)2, which are monosubstituted at the 6-position on the pyridine ring, or -CH3, -N(CH3)2, or -CF3, which are monosubstituted at the 4-position on the pyridine ring, or the same or different -CH3, -CH2CH3, -CH5, -CH(CH6H5)2, -N(CH3)2, or -CF3, which are disubstituted at the 4- and 6-positions on the pyridine ring; R5 is -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH6H5, or -CH(CH6H5)2 monosubstituted at the 4-position on the dihydrooxazole ring; R2, R4, and R6 are each independently H, or -Cl, -F, -CH3, -OCH3, -N(CH3)2, or -CF3 monosubstituted at the 4-position on the pyridine ring. R7 is H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -Cl, -C6H5, or -CH(C6H5)2.

[0014] A third aspect of the present invention provides a copolymer prepared by the preparation method of the present invention.

[0015] A fourth aspect of the present invention provides a vulcanizate prepared with the copolymer of the present invention.

[0016] A fifth aspect of the present invention provides the use of the vulcanized rubber of the present invention in a tire, a shoe sole, a conveyor belt, a hose, or a gasket.

[0017] [Effects of the Invention] With the above technical solutions, the present invention has the following advantages over the prior art:

[0018] The present invention synthesizes a copolymer by in-situ polymerization. The copolymer is a block copolymer containing polyethylene segments and butadiene rubber segments, with relatively long methylene sequences. The polyethylene butadiene rubber block copolymer acts as a solubilizer, promoting dissolution of the polyethylene phase of the reinforcement and the butadiene rubber matrix, resulting in a copolymer with good reinforcing filler dispersion without the need for subsequent compounding. This solves the problems of phase separation and interfacial deficiency that exist in blends. Furthermore, the relatively long methylene sequences are regularly arranged, resulting in the formation of crystalline regions in the copolymer segments, providing a reinforcing effect for the butadiene rubber.

[0019] This invention employs a single-step polymerization process using a catalyst. By selecting a catalyst with a specific structure, it is possible to simultaneously synthesize two conventional polymers, polyethylene (resin) and butadiene rubber (rubber), while also significantly increasing the length of consecutive methylene sequences in the resulting copolymer. Compared to stepwise polymerization methods, this invention offers advantages such as simpler processes, greater operability, lower costs, and easier control of the polymerization process and composite composition, making it favorable for industrial production.

[0020] Other features and advantages of the present invention are described in detail in the detailed description that follows.

[0021] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] DSC chart (above room temperature) of the copolymer prepared in Example 1. FIG. 2 is an infrared spectrum of the copolymer prepared in Example 1. [Figure 3] DSC chart (above room temperature) of the copolymer prepared in Example 11. FIG. 4 is an infrared spectrum of the copolymer prepared in Example 11. [Figure 5] Nuclear magnetic resonance hydrogen spectrum of the copolymer prepared in Example 6. FIG. 6 is a TEM of the copolymers prepared in Comparative Example 6 (left) and Example 6 (right). FIG. 7 is a COSY spectrum of the copolymer prepared in Example 3.

[0022] [Mode for Carrying Out the Invention] The endpoints of the ranges and any values ​​disclosed herein should be understood not to be limited to the exact range or value, but to include values ​​close to these ranges or values. In the case of numerical ranges, the endpoints of each range, the endpoints of each range and individual dot values, and the individual dot values ​​can be combined to obtain one or more new numerical ranges, which are considered to be specifically disclosed herein.

[0023] A first aspect of the present invention provides a copolymer, the copolymer being a block copolymer and comprising a polyethylene segment and a butadiene rubber segment, wherein a weight ratio of the polyethylene segment to the butadiene rubber segment, based on the total amount of the copolymer, is 0.1:99.9 to 80:20, and the butadiene rubber segment has a cis 1,4-structure content of 90 to 98.5 mol%, a trans 1,4-structure content of 0.9 to 5.7 mol%, and a 1,2-structure content of 0.6 to 4.3 mol%, based on the total amount of the butadiene rubber segment, and a length of consecutive methylene sequences in the copolymer is at least 165.

[0024] The copolymer according to the present invention is a butadiene rubber (i.e., cis-1,4-polybutadiene rubber) that incorporates polyethylene segments formed from ethylene structural units in addition to cis-1,4-butadiene structural units (which can form butadiene rubber segments), thereby forming a block copolymer structure containing cis-1,4-butadiene structural unit segments and ethylene structural unit segments, thereby achieving modification of the butadiene rubber segments and improving the tensile strength and tear resistance shortcomings of existing butadiene rubber materials. Specifically, in the present invention, the length of consecutive methylene sequences in the copolymer is at least 165, which further enhances the compatibility between the polyethylene segments and the butadiene rubber segments, allows the resin phase and the rubber phase to be uniformly mixed, and allows the resin phase to better reinforce the rubber phase.

[0025] Furthermore, when the weight ratio of the polyethylene segment to the butadiene rubber segment in the copolymer and the contents of the cis 1,4-structure, trans 1,4-structure, and 1,2-structure in the butadiene rubber segment satisfy the above ranges, the elasticity of the rubber phase and the reinforcement by the resin phase can be achieved at the same time, which is more suitable for the actual application needs of the copolymer.

[0026] In some preferred embodiments of the present invention, the weight ratio of the polyethylene segment to the butadiene rubber segment is preferably 1:99 to 75:25 based on the total amount of the copolymer.

[0027] In some preferred embodiments of the present invention, the length of the consecutive methylene sequences in the copolymer is preferably 250 to 1,800.

[0028] The butadiene rubber segment contained in the copolymer according to the present invention may have a structure obtained by 1,4 addition polymerization or a structure obtained by 1,2 polymerization, thereby providing the copolymer with improved final properties. In some preferred embodiments, the butadiene rubber segment preferably has a cis-1,4-structure content of 92 to 98 mol% based on the total amount of the butadiene rubber segment.

[0029] In some preferred embodiments of the present invention, the butadiene rubber segment has a trans 1,4-structural unit content of 1.2 to 4.8 mol % based on the total amount of the butadiene rubber segment.

[0030] In some preferred embodiments of the present invention, the butadiene rubber segment has a 1,2-structural unit content of 0.8 to 3.2 mol % based on the total amount of the butadiene rubber segment.

[0031] The copolymer according to the present invention has the above structure, and in some preferred embodiments, the copolymer preferably has a melting temperature Tm of 120 to 150°C and a crystallinity of 0.2 to 80%, preferably a Tm of 125 to 145°C and a crystallinity of 0.5 to 65%. The above properties of the copolymer can be measured by DSC.

[0032] The copolymer according to the present invention preferably has a glass transition temperature Tg of -120°C to -95°C, more preferably -115°C to -100°C.

[0033] In the copolymer according to the present invention, the crystallization temperature Tc of the copolymer is preferably 100°C to 125°C, and more preferably 105°C to 122°C.

[0034] The copolymer according to the present invention preferably has a number average molecular weight of 50,000 g / mol to 800,000 g / mol and a molecular weight distribution of 2 to 7, and more preferably has a number average molecular weight of 100,000 g / mol to 700,000 g / mol and a molecular weight distribution of 2.5 to 6.5. The above properties of the copolymer can be measured by GPC.

[0035] A second aspect of the present invention provides a method for preparing a copolymer, the method comprising: Step (1) is a step of polymerizing ethylene in the presence of an organic solvent, a catalyst, and an aluminum-containing cocatalyst-1 to obtain a polyethylene product, wherein the polymerization temperature is 20 to 70°C, the ethylene pressure is maintained at 1 to 70 bar, and the polymerization time is 1 to 80 minutes; (2) introducing 1,3-butadiene monomer into the polyethylene product and removing unreacted ethylene monomer; and step (3) adding a chloroaluminum-containing cocatalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between 1,3-butadiene monomer and the polyethylene active segments in the polyethylene product, thereby obtaining the copolymer; The catalyst is at least one selected from the compounds represented by formula 1, formula 2, and formula 3.

[0036] [ka]

[0037] (wherein X is chlorine or bromine, R1 is a substituent mono-substituted at the 2- or 4-position on the benzene ring, or identical or different substituents di-substituted at the 2-, 4-, or 2-, 6-positions on the benzene ring, or identical or different substituents tri-substituted at the 2-, 4-, and 6-positions on the benzene ring, wherein the substituents are -F, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH6H5, or -CH(CH6H5)2; R3 is -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH6H5, or -CH(CH6H5)2, which are monosubstituted at the 6-position on the pyridine ring, or -CH3, -N(CH3)2, or -CF3, which are monosubstituted at the 4-position on the pyridine ring, or the same or different -CH3, -CH2CH3, -CH5, -CH(CH6H5)2, -N(CH3)2, or -CF3, which are disubstituted at the 4- and 6-positions on the pyridine ring; R5 is -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH6H5, or -CH(CH6H5)2 monosubstituted at the 4-position on the dihydrooxazole ring; R2, R4, and R6 are each independently H, or -Cl, -F, -CH3, -OCH3, -N(CH3)2, or -CF3 monosubstituted at the 4-position on the pyridine ring.

[0038] R7 is H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -Cl, -C6H5, or -CH(C6H5)2. In the present invention, ethylene polymerization and polyethylene copolymerization with 1,3-butadiene monomer are sequentially carried out in the presence of a catalyst system containing a cobalt-based catalyst including a cobalt organic compound, and in the resulting high polymer, polyethylene and polybutadiene segments are chemically bonded to obtain a block copolymer containing polyethylene segments and butadiene rubber segments, thereby improving the properties of butadiene rubber.

[0039] Specifically, in the present invention, by selecting the above catalyst having a specific structure and controlling the conditions for the ethylene polymerization reaction, it is possible not only to simultaneously synthesize two conventional polymers, polyethylene and butadiene rubber, but also to significantly increase the length of consecutive methylene sequences in the resulting copolymer compared to prior art, thereby further improving the properties of butadiene rubber.

[0040] Furthermore, in the copolymerization reaction stage of polyethylene and 1,3-butadiene, chloroaluminum-containing cocatalyst-2 is added. The chloroaluminum-containing cocatalyst-2 has a certain electron-donating effect, which is favorable for the formation of a η3 coordination environment for 1,3-butadiene, and favors the progress of 1,4-polymerization of 1,3-butadiene.

[0041] In some embodiments of the present invention, R represents a substituent on the benzene ring of formula 1, and R represents a substituent other than H at some of the substitution positions on the benzene ring, and as described above, R represents a mono-substitution at the 2- or 4-position on the benzene ring, or a di-substitution at the 2-, 4-, or 2-, 6-positions on the benzene ring, or a tri-substitution at the 2-, 4-, and 6-positions on the benzene ring, and the other substitution positions are H, where in the case of di- and tri-substitution, the substituents may be the same or different, and preferably -F, - which are mono-substituted at the 2- or 4-position on the benzene ring. or -CH(CH)2, -C(CH)3, -CHH, or -CH(CH)2, or -F, -CH, -CHCH, -CH(CH)2, -C(CH)3, -CHH, or -CH(CH)2, disubstituted at the 2-, 4-, or 2-, 6-positions on the benzene ring, or -F, -CH, -CHCH, -CH(CH)2, -C(CH)3, -CHH, or -CH(CH)2, trisubstituted at the 2-, 4-, or 6-positions on the benzene ring, more particularly Groups represented by substitution positions on the Zene ring: 2-F-, 2-CH3-, 4-F-, 4-CH3-, 2,4-F-, 2,4-CH3-, 2,6-F-, 2,6-CH3-, 2,4,6-F-, 2,4,6-CH3-, 2-CH2CH3-, 4-CH2CH3-, 2,4-CH2CH3-, 2-CH2CH3-4-CH3-, 2,6-CH2CH3-, 2-CH2CH3-6-CH3-, 2,4,6-CH2CH3-, 2-CH(CH3)2-, 4-CH(CH3)2-, 2,4-CH(CH3)2-, 2,6-CH(CH3) It has one of 2-, 2,4,6-CH(CH3)2-, 2-C(CH3)3-, 4-C(CH3)3-, 2,4-C(CH3)3-, 2,6-C(CH3)3-, 2-C(CH3)3-6-CH3-, 2,4,6-C(CH3)3-, 2-C6H5-, 4-C6H5-, 2,4-C6H5-, 2,6-C6H5-, 2,4,6-C6H5-, 2-CH(C6H5)2-, 4-CH(C6H5)2-, 2,4-CH(C6H5)2-, 2,6-CH(C6H5)2-, and 2,4,6-CH(C6H5)2-.

[0042] In some embodiments of the present invention, R3 represents a substituent on the pyridine ring of formula 2 (other than the R4-substituted pyridine ring), and R3 represents a substituent other than H at some of the substitution positions on the pyridine ring, and as described above, R3 represents a mono-substitution at the 4- or 6-position on the pyridine ring, or a di-substitution at the 4- and 6-positions on the pyridine ring, with the other substitution positions being H, where in the case of di-substitution, the substituents may be the same or different, and are preferably -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH5, or -CH(CH6H5)2 mono-substituted at the 6-position on the pyridine ring, or -CH3, -N(CH3)2, or -CF3 mono-substituted at the 4-position on the pyridine ring, or -CH3, -CH2CH3, -C(CH3)3, -CH5, or -CH(CH6H5)2 di-substituted at the 4- and 6-positions on the pyridine ring. 6H5, -CH(C6H5)2, -N(CH3)2 or -CF3, and more specifically, groups represented by the substitution positions on the pyridine ring: 6-CH3-, 6-CH2CH3-, 6-C6H5-, 6-CH(C6H5)2-, 4-CH3-, 4-N(CH3)2-, 4-CF3-, 4,6-CH3-, 4-CH3-6-CH2CH3-, 4-CH3-6-C6H5-, 4-CH It has one of 3-6-CH(C6H5)2-, 4-N(CH3)2-6-CH3-, 4-N(CH3)2-6-CH2CH3-, 4-N(CH3)2-6-C6H5-, 4-N(CH3)2-6-CH(C6H5)2-, 4-CF3-6-CH3-, 4-CF3-6-CH2CH3-, 4-CF3-6-C6H5-, 4-CF3-6-CH(C6H5)2-.

[0043] In some embodiments of the present invention, R5 represents a substituent on the dihydrooxazole ring of Formula 3, and R5 represents a substituent other than H at some of the substitution positions on the dihydrooxazole ring, and as described above, represents a mono-substitution at the 4-position on the dihydrooxazole ring and H at other substitution positions, preferably -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -CH5, or -CH(CH6H5)2 mono-substituted at the 4-position on the dihydrooxazole ring, more specifically, one of the groups represented by the substitution positions on the dihydrooxazole ring: 4-CH3-, 4-CH2CH3-, 4-CH(CH3)2-, 4-C(CH3)3-, 4-CH5-, 4-CH(CH6H5)2-.

[0044] In some embodiments of the present invention, R2, R4, and R6 each represent a substituent on the pyridine ring of Formulas 1, 2, and 3 (other than the R3-substituted pyridine ring in Formula 2), and the multiple substitution positions on the pyridine ring substituted by R2, R4, and R6 may all be H. Preferably, R2, R4, and R6 are each H. Alternatively, R2, R4, and R6 each represent -Cl, -F, -CH3, -OCH3, -N(CH3)2, or -CF3 substituted at the 4-position on the substituted pyridine ring, more specifically, one of the groups represented by the substitution positions on the pyridine ring: 4-Cl-, 4-F-, 4-CH3-, 4-OCH3-, 4-N(CH3)2-, and 4-CF3-. R2, R4, and R6 may be the same or different.

[0045] In some embodiments of the invention, R7 represents a substituent of Formula 1. Preferably, R7 is H, -CH3, -CH2CH3, -Cl, or -C6H5.

[0046] In some embodiments of the present invention, the aluminum-containing cocatalyst-1 is preferably at least one selected from methylaluminoxane (MAO), triisobutylaluminum-modified methylaluminoxane (MMAO), diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride, and is preferably at least one selected from methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, diisobutylaluminum chloride, ethylaluminum dichloride, and sesquiethylaluminum.Initiation of the polymerization reaction of ethylene monomer is realized.

[0047] In some embodiments of the present invention, the chloroaluminum-containing cocatalyst-2 is preferably at least one selected from diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride, preferably diisobutylaluminum chloride, ethylaluminum dichloride, or sesquiethylaluminum, which initiates the copolymerization reaction of 1,3-butadiene monomer and polyethylene.

[0048] In some embodiments of the present invention, the molar ratio of the catalyst to aluminum-containing cocatalyst-1 to chloroaluminum-containing cocatalyst-2 is preferably 1:(15-1,000):(20-1,000), and more preferably 1:20-900:40-900. In the present invention, by controlling the molar ratios of the catalyst to aluminum-containing cocatalyst-1 and chloroaluminum-containing cocatalyst-2 so as to satisfy the above ranges, it is possible to control the reaction activity of each of the polymerization reaction and copolymerization reaction in steps (1) and (3), and to control the contents of ethylene structural segments and butadiene structural segments in the resulting copolymer, the content of cis-1,4-structures, and the length of consecutive methylene sequences in the copolymer.

[0049] In some embodiments of the present invention, preferably the organic solvent is at least one selected from n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decalin, dodecane, hydrogenated gasoline, preferably toluene.

[0050] In some embodiments of the present invention, in step (1), the polymerization temperature is preferably 30 to 60°C, the ethylene pressure is maintained at 2.5 to 50 bar, and the polymerization time is 2 to 60 minutes. The pressure may be the gas phase pressure of the supplied ethylene monomer.

[0051] In some embodiments of the present invention, in step (3), the concentration of 1,3-butadiene in the polymerization system obtained in step (2) is preferably 0.4 to 12 mol / L, preferably 0.6 to 9 mol / L, the copolymerization temperature is 30 to 70°C, preferably 40 to 60°C, the copolymerization pressure is 1 to 10 bar, preferably 2 to 5 bar, and the copolymerization time is 0.5 to 5 hours, preferably 1 to 4 hours. The pressure may be the gas phase pressure of the supplied 1,3-butadiene monomer. The concentration of 1,3-butadiene is limited to limit the amount of solvent used.

[0052] In some embodiments of the present invention, preferably, in step (3), the molar ratio of the catalyst to 1,3-butadiene is 1:1,000-10,000; preferably 1:1,200-8,000.

[0053] In some embodiments of the present invention, the relationship between the amount of ethylene monomer and butadiene used can be controlled by adjusting the reaction time and pressure during the introduction of ethylene monomer, thereby obtaining a composite material with butadiene rubber as the elastomer substrate and polyethylene as the reinforcing phase. Preferably, the relationship between the weights of ethylene monomer and butadiene monomer supplied satisfies the corresponding amounts of polyethylene segments and butadiene rubber segments in the resulting copolymer. For example, the weight ratio of the polyethylene segments to the butadiene rubber segments, based on the total amount of the copolymer, is 0.1:99.9 to 80:20, preferably 1:99 to 75:25. The content of cis-1,4-structures in the butadiene rubber segments, based on the total amount of the butadiene rubber segments, is 90 to 98.5 mol%, preferably 92 to 98 mol%, and the length of consecutive methylene sequences in the copolymer is at least 165, preferably 250 to 1,800.

[0054] In the present invention, when it is necessary to terminate the copolymerization reaction, the following steps may be carried out.

[0055] When the copolymerization reaction has progressed to an appropriate time, a stabilizer and a terminator are added in that order to terminate the copolymerization reaction, and the resulting product is then washed and dissolved, and then vacuum dried to obtain the ethylene-reinforced butadiene rubber.

[0056] The stabilizer may be a reagent that acts as an antioxidant, such as a 5% toluene solution of 2,2-methylenebis-(4-methyl-6-tert-butylphenol), added in an amount of 0.5 wt% to 1 wt% of the total weight of the monomers. The terminator may be a reagent that terminates polymerization and removes residual catalyst, such as a 4% hydrochloric acid methanol solution, added in an amount of 0.1 wt% to 1 wt% of the total weight of the monomers. The washing process may involve washing with a methanol solution and water three times in succession.

[0057] The preparation method according to the present invention specifically includes:

[0058] The polymerization reaction environment in the reactor is purified by the Schlenk method. The cobalt-based catalyst and organic solvent of the present invention are added to the reactor, stirred to uniformly disperse, and heated to a set temperature. Ethylene monomer is then introduced into the reactor at a pressure of 1 to 70 bar. After maintaining a constant pressure, a predetermined amount of aluminum-containing cocatalyst-1 is added to initiate the ethylene polymerization reaction. The polymerization reaction time is determined based on the content of ethylene segments in the final copolymer.

[0059] After the set polymerization reaction time has elapsed, the introduction of ethylene monomer is stopped, purified 1,3-butadiene monomer is added, residual ethylene monomer is removed, the pressure is adjusted to 1-10 bar, and aluminum-containing cocatalyst-2 is added to initiate the copolymerization reaction of 1,3-butadiene monomer and polyethylene active segments, and a constant pressure is maintained for the set time.

[0060] Finally, a stabilizer and a terminator are added to terminate the reaction, and the resulting product is then washed and dissolved three times with a methanol solution and an organic solvent, and then dried in a vacuum to obtain the butadiene rubber in-situ reinforced with the polyethylene.

[0061] A third aspect of the present invention provides a copolymer prepared by the preparation method of the present invention.

[0062] In some embodiments of the present invention, the copolymer is preferably as described above and will not be described in detail.

[0063] A fourth aspect of the present invention provides a vulcanizate prepared with the copolymer of the present invention.

[0064] A fifth aspect of the present invention provides the use of the vulcanized rubber of the present invention in a tire, a shoe sole, a conveyor belt, a hose, or a gasket.

[0065] In order to clearly illustrate the reaction process of the present invention, the preparation method of the copolymer is described in detail below with reference to examples, but the following examples do not limit the entire protection scope of the present invention.

[0066] In the following examples and comparative examples, DSC data were measured using a PerkinElmer DSC8000 differential thermal analyzer, and the test conditions included: accurately weighing approximately 5-10 mg of sample, maintaining a nitrogen atmosphere throughout the process, and first heating the polymer to 200-220°C at a rate of 10°C / min, keeping the temperature constant for 2 minutes to remove the thermal history, then cooling to 50°C at a rate of 10°C / min, and finally heating again to 210°C at the same rate.

[0067] Copolymer samples were subjected to sequential self-nucleation and annealing heat treatments (SNA) to grade different lengths of consecutive methylene chains (MSLs) according to the procedure described in "Quantitative Determination of Short-Chain Branching Content and Distribution in Commercial Polyethylenes by Thermally Fractionated Differential Scanning Calorimetry" by M. Zhang and S.E. Wanke (Polymer Engineering & Science, 2003, 43, 1878-1888). Groups of segments with similar lengths of consecutive methylene chains produce crystals of similar size and melt at similar temperatures (F.M. Mirabella, J. Polyrn Sci: Part B: Polym Phys., 2001, 39, 2800). The melting endothermic peaks of the polymers were then measured by differential scanning calorimetry (DSC) according to GB / T 29611-201, with each endothermic peak corresponding to a corresponding length of consecutive methylene chains. The length of the consecutive methylene sequences in the copolymer is calculated according to formula (I).

[0068]

number

[0069] GPC data was measured using a PL triple detector, and the test conditions included the following: the sample was dissolved in trichlorobenzene (1 mg / mL) at 150°C (polystyrene as standard).

[0070] The breaking strength of vulcanized rubber was tested in accordance with the national standard "GB / T528-2009" using a tensile testing machine model AG-20KNG manufactured by Shimadzu Corporation. The tear strength was tested in accordance with the national standard "GB / T529-2008" using a tensile testing machine model AG-20KNG manufactured by Shimadzu Corporation.

[0071] Infrared spectrum testing is performed by ATR-FTIR method using a Nicolet 6700 infrared spectrometer.

[0072] NMR spectrograms were recorded using a Unity-400 NMR instrument from Varian, USA, and the solvent was deuterated chloroform or deuterated tetrachloroethane. 1 H NMR (400 MHz), 13 C NMR (100 MHz) and COSY were recorded at room temperature, with TMS used as the internal standard.

[0073] TEM is performed using a Tecnai G2 F20 S-TWIN transmission electron microscope, and samples are tested after OsO4 staining and sectioning.

[0074] Example 1 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH(CH3)2- (all other substituents on the benzene ring are hydrogen), R2 is hydrogen (all substituents on the pyridine ring are hydrogen), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 30 °C and maintained at a constant pressure (4 bar) of ethylene monomer. Then, methylaluminoxane (MAO) (0.679 mol) was added to initiate the polymerization of ethylene. After 5 min of polymerization, the introduction of ethylene monomer was stopped.

[0075] 1,3-Butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After complete removal of the ethylene monomer, 5.56 mol of 1,3-butadiene was added. A constant pressure (3 bar) atmosphere was maintained, and diisobutylaluminum chloride (0.679 mol) was injected to initiate the butadiene copolymerization. The copolymerization temperature was 45°C and the copolymerization time was 2 h. Next, a 5% toluene solution of 2,2-methylenebis(4-methyl-6-tert-butylphenol) was added as a stabilizer. Then, 20 mL of a 4% hydrochloric acid solution in methanol was added to the polymerization system to terminate the reaction. Finally, the polymerization product was washed three times with methanol and then vacuum dried to yield 255.9 g of copolymer. The molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:300:300, and the molar ratio of catalyst:1,3-butadiene was 1:2460.

[0076] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained, as shown in Figure 2, shows the characteristic peaks of butadiene rubber at wavenumbers 1650 and 736, and the characteristic peak of the polyethylene segment at wavenumber 720.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows the butadiene rubber peak at chemical shift 5.4 and the ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 3.5 wt%, and the butadiene rubber segment content is 96.5 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 97.7 mol%, the trans 1,4-structure content is 1.4 mol%, and the 1,2-structure content is 0.9 mol%.

[0077] DSC test data: As can be seen from Figure 1, the copolymer has a Tg of -109.9°C, a Tm of 133.4°C, a Tc of 118.3°C, a crystallinity of 2.5%, and a length of consecutive methylene sequences of 261 to 412. GPC test data: The copolymer has a number average molecular weight of 174,000 g / mol and a molecular weight distribution of 2.93. The structure and physical and chemical parameters of the copolymer are shown in Table 2.

[0078] Example 2 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH(CH3)2- (other substituents on the benzene ring are H), R2 is 4-OCH3- (other substituents on the pyridine ring are H), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 39 °C and maintained at a constant pressure of ethylene monomer (4.9 bar). Then, methylaluminoxane (MAO) (1.36 mol) was added to initiate the polymerization of ethylene. After 2 min of polymerization, the introduction of ethylene monomer was stopped.

[0079] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 9.26 mol of 1,3-butadiene was added. A constant pressure (2 bar) atmosphere was maintained, and diisobutylaluminum chloride (0.679 mol) was injected to initiate the copolymerization of butadiene. The copolymerization temperature was 48°C, and the copolymerization time was 4 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:602:300, and the molar ratio of catalyst:1,3-butadiene was 1:4097.

[0080] The polymerization product was post-treated according to the method of Example 1 to obtain 485.9 g of copolymer.

[0081] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1644 and 734, and a characteristic peak of a polyethylene segment at wavenumber 719.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 1.3 wt%, and the butadiene rubber segment content is 98.7 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 98.0 mol%, the trans 1,4-structure content is 1.2 mol%, and the 1,2-structure content is 0.8 mol%.

[0082] The DSC test data show that the copolymer has a Tg of -111.7°C, a Tm of 127.3°C, a Tc of 109.6°C, a crystallinity of 0.9%, and a length of consecutive methylene sequences of 165 to 264. GPC test data show that the copolymer has a number average molecular weight of 336,000 g / mol and a molecular weight distribution of 2.75.

[0083] Example 3 (1) After cycling the polymerization reactor three times using the Schlenk method, 3 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,4,6-CH3- (other substituents on the benzene ring are H), R2 is 4-F- (other substituents on the pyridine ring are H), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 35°C, and under a constant pressure (4 bar) of ethylene monomer, diethylaluminum chloride (0.113 mol) was added to initiate ethylene polymerization. After 10 min of polymerization, the introduction of ethylene monomer was stopped.

[0084] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 12 mol of 1,3-butadiene was added. A constant pressure (4 bar) atmosphere was maintained, and diisobutylaluminum chloride (0.679 mol) was injected to initiate the copolymerization of butadiene. The copolymerization temperature was 50°C, and the copolymerization time was 2 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:50:300, and the molar ratio of catalyst:1,3-butadiene was 1:5310.

[0085] The polymerization product was post-treated according to the method of Example 1 to obtain 595.1 g of copolymer.

[0086] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1644 and 738, and a characteristic peak of a polyethylene segment at wavenumber 720.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 1.7 wt%, and the butadiene rubber segment content is 98.3 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 97.8 mol%, the trans 1,4-structure content is 1.3 mol%, and the 1,2-structure content is 0.9 mol%.

[0087] The DSC test data show that the copolymer has a Tg of -107.9°C, a Tm of 129.4°C, a Tc of 111.5°C, a crystallinity of 1.2%, and a length of consecutive methylene sequences of 182 to 302. GPC test data show that the copolymer has a number average molecular weight of 411,000 g / mol and a molecular weight distribution of 2.82.

[0088] Example 4 (1) After cycling the polymerization reactor three times using the Schlenk method, 4 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-F- (other substituents on the benzene ring are H), R2 is 4-CF3- (other substituents on the pyridine ring are H), R7 is ethyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 30 °C and maintained at a constant pressure of 24 bar. Then, methylaluminoxane (MAO) (0.679 mol) was added to initiate the polymerization of ethylene. After 7 min of polymerization, the introduction of ethylene monomer was stopped.

[0089] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 17.2 mol of 1,3-butadiene was added. A constant pressure (2.5 bar) was maintained, and diisobutylaluminum chloride (0.679 mol) was added to initiate the copolymerization of butadiene. The copolymerization temperature was 50°C, and the copolymerization time was 4 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:300:300, and the molar ratio of catalyst:1,3-butadiene was 1:7611.

[0090] The polymerization product was post-treated according to the method of Example 1 to obtain 995.1 g of copolymer.

[0091] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 741, and a characteristic peak of a polyethylene segment at wavenumber 722.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 8.2 wt%, and the butadiene rubber segment content is 91.8 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 96.5 mol%, the trans 1,4-structure content is 2.2 mol%, and the 1,2-structure content is 1.3 mol%.

[0092] The DSC test data show that the copolymer has a Tg of -113.9°C, a Tm of 132.8°C, a Tc of 114.1°C, a crystallinity of 6.1%, and a length of consecutive methylene sequences of 243 to 394. GPC test data: the copolymer has a number average molecular weight of 677,000 g / mol and a molecular weight distribution of 3.11.

[0093] Example 5 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH2CH3- (other substituents on the benzene ring are H), R2 is 4-CH3- (other substituents on the pyridine ring are H), R7 is H, and X is bromine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 40 °C and maintained at a constant pressure of ethylene monomer (5.9 bar). Then, methylaluminoxane (MAO) (1.131 mol) was added to initiate ethylene polymerization. The reaction time was 9 min. The introduction of ethylene monomer was then stopped.

[0094] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 3.7 mol of 1,3-butadiene was added. A constant pressure (5 bar) atmosphere was maintained, and diisobutylaluminum chloride (1.131 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 52°C, and the copolymerization reaction time was 1 hour. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:500:500. The molar ratio of catalyst: 1,3-butadiene was 1:1637.

[0095] The polymerization product was post-treated according to the method of Example 1 to obtain 201.7 g of copolymer.

[0096] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1649 and 741, and a characteristic peak of a polyethylene segment at wavenumber 721.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 5.7 wt%, and the butadiene rubber segment content is 94.3 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 97.2 mol%, the trans 1,4-structure content is 1.7 mol%, and the 1,2-structure content is 1.1 mol%.

[0097] The DSC test data show that the copolymer has a Tg of -106.9°C, a Tm of 134.2°C, a Tc of 115.9°C, a crystallinity of 4.2%, and a length of consecutive methylene sequences of 271 to 446. GPC test data show that the copolymer has a number average molecular weight of 142,000 g / mol and a molecular weight distribution of 3.04.

[0098] Example 6 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH2CH3- (other substituents on the benzene ring are H), R2 is 4-N(CH3)2- (other substituents on the pyridine ring are H), R7 is phenyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 33 °C and maintained at a constant pressure (5 bar) of ethylene monomer. Then, modified methylaluminoxane (MMAO) (1.584 mol) was added to initiate ethylene polymerization. The reaction time was 18 min. The introduction of ethylene monomer was then stopped.

[0099] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 5.19 mol of 1,3-butadiene was added. A constant pressure (3 bar) atmosphere was maintained, and diisobutylaluminum chloride (1.584 mol) was injected to initiate the copolymerization of butadiene. The copolymerization temperature was 53°C, and the copolymerization time was 2 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:701:701, and the molar ratio of catalyst:1,3-butadiene was 1:2296.

[0100] The polymerization product was post-treated according to the method of Example 1 to obtain 301.7 g of copolymer.

[0101] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1648 and 737, and a characteristic peak of a polyethylene segment at wavenumber 723.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10, as shown in Figure 5.); The polyethylene segment content is 12.9 wt%, and the butadiene rubber segment content is 87.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 96.0 mol%, the trans 1,4-structure content is 2.6 mol%, and the 1,2-structure content is 1.4 mol%.

[0102] The DSC test data show that the copolymer has a Tg of -110.1°C, a Tm of 136.7°C, a Tc of 115.2°C, a crystallinity of 9.7%, and a length of consecutive methylene sequences of 361 to 592. GPC test data show that the copolymer has a number average molecular weight of 208,000 g / mol and a molecular weight distribution of 3.40.

[0103] Example 7 (1) After the polymerization reactor was cycled three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2-C(CH3)3-6-CH3- (other substitutions on the benzene ring are H), R2 is 4-Cl- (other substitutions on the pyridine ring are H), R7 is chlorine, and X is bromine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 37°C, and while maintaining a constant pressure (4 bar) of ethylene monomer, diethylaluminum chloride (45.2 mmol) was added to initiate ethylene polymerization. The reaction time was 60 min. The introduction of ethylene monomer was then stopped.

[0104] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 8.3 mol of 1,3-butadiene was added. A constant pressure (2.2 bar) was maintained, and diisobutylaluminum chloride (2.036 mol) was injected to initiate the copolymerization of butadiene. The copolymerization temperature was 54°C, and the copolymerization time was 3 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:20:901, and the molar ratio of catalyst:1,3-butadiene was 1:3673.

[0105] The polymerization product was post-treated according to the method of Example 1 to obtain 502.3 g of copolymer.

[0106] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1639 and 740, and a characteristic peak of a polyethylene segment at wavenumber 722.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 4.9 wt%, and the butadiene rubber segment content is 95.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 95.8 mol%, the trans 1,4-structure content is 2.7 mol%, and the 1,2-structure content is 1.5 mol%.

[0107] The DSC test data show that the copolymer has a Tg of -108.5°C, a Tm of 133.2°C, a Tc of 112.5°C, a crystallinity of 3.6%, and a length of consecutive methylene sequences of 247 to 408. GPC test data show that the copolymer has a number average molecular weight of 350,000 g / mol and a molecular weight distribution of 2.97.

[0108] Example 8 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by formula 2 (where R3 is 4,6-CH3- (all other substitution positions on the pyridine ring substituted by R3 are H), R4 is H (all substitution positions on the pyridine ring substituted by R4 are H), and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 60 °C and maintained at a constant pressure (50 bar) of ethylene monomer. Then, methylaluminoxane (0.113 mol) was added to initiate ethylene polymerization. The introduction of ethylene monomer was stopped after the reaction time reached 19 min.

[0109] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 5.56 mol of 1,3-butadiene was added. A constant pressure (3.5 bar) was maintained, and diisobutylaluminum chloride (1.584 mol) was injected to initiate the copolymerization of butadiene. The copolymerization temperature was 58°C, and the copolymerization time was 3.5 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:50:701, and the molar ratio of catalyst:1,3-butadiene was 1:2460.

[0110] The polymerization product was post-treated according to the method of Example 1 to obtain 491.1 g of copolymer.

[0111] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1639 and 739, and a characteristic peak of a polyethylene segment at wavenumber 720.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 57.9 wt%, and the butadiene rubber segment content is 42.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 93.2 mol%, the trans 1,4-structure content is 4.2 mol%, and the 1,2-structure content is 2.6 mol%.

[0112] The DSC test data show that the copolymer has a Tg of -110.9°C, a Tm of 139.2°C, a Tc of 118.8°C, a crystallinity of 46.3%, and a length of consecutive methylene sequences of 539 to 860. GPC test data show that the copolymer has a number average molecular weight of 333,000 and a molecular weight distribution of 5.10.

[0113] Example 9 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 2 (where R3 is 4-N(CH3)2-6-CH2CH3- (other substitutions on the pyridine ring substituted by R3 are H), R4 is 4-OCH3- (other substitutions on the pyridine ring substituted by R4 are H), and X is bromine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 50 °C and maintained at a constant pressure (8 bar) of ethylene monomer. Diethylaluminum chloride (0.684 mol) was added to initiate ethylene polymerization. The reaction time reached 16 min, after which the introduction of ethylene monomer was stopped.

[0114] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 8.61 mol of 1,3-butadiene was added. A constant pressure (3.5 bar) was maintained, and diisobutylaluminum chloride (0.684 mol) was injected to initiate the copolymerization of butadiene monomer. The copolymerization temperature was 60°C, and the copolymerization time was 3.8 h. The molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:303:303. The molar ratio of catalyst:1,3-butadiene was 1:3810.

[0115] The polymerization product was post-treated according to the method of Example 1 to obtain 468.3 g of copolymer.

[0116] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1649 and 729, and a characteristic peak of a polyethylene segment at wavenumber 719.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 26.5 wt%, and the butadiene rubber segment content is 73.5 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 94.7 mol%, the trans 1,4-structure content is 3.2 mol%, and the 1,2-structure content is 2.1 mol%.

[0117] The DSC test data of the in-situ reinforced butadiene rubber shows Tg = -106.4°C, Tm = 137.7°C, Tc = 117.2°C, a crystallinity of 20.2%, and a length of consecutive methylene sequences of 417 to 672. GPC test data: The copolymer has a number average molecular weight of 314,000 g / mol and a molecular weight distribution of 4.03.

[0118] Example 10 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 2 (where R3 is 4-CF3-6-CH5- (other substitutions on the pyridine ring substituted by R3 are H), R4 is 4-F- (other substitutions on the pyridine ring substituted by R4 are H), and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 55 °C and maintained at a constant pressure (4 bar) of ethylene monomer. Then, methylaluminoxane (MAO) (1.584 mol) was added to initiate the polymerization of ethylene. After 7 min of polymerization, the introduction of ethylene monomer was stopped.

[0119] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 3.33 mol of 1,3-butadiene was added. A constant pressure (2.5 bar) atmosphere was maintained, and diisobutylaluminum chloride (1.584 mol) was injected to initiate the continuous copolymerization of butadiene. The copolymerization temperature was 55°C, and the copolymerization time was 1 hour. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:701:701. The molar ratio of catalyst: 1,3-butadiene was 1:1473.

[0120] The polymerization product was post-treated according to the method of Example 1 to obtain 191.1 g of copolymer.

[0121] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1646 and 741, and a characteristic peak of a polyethylene segment at wavenumber 722.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 41.9 wt%, and the butadiene rubber segment content is 58.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 93.8 mol%, the trans 1,4-structure content is 3.8 mol%, and the 1,2-structure content is 2.4 mol%.

[0122] The DSC test data show that the copolymer has a Tg of -102.5°C, a Tm of 138.6°C, a Tc of 116.9°C, a crystallinity of 32.7%, and a length of consecutive methylene sequences of 475 to 780. GPC test data show that the copolymer has a number average molecular weight of 139,000 g / mol and a molecular weight distribution of 4.62.

[0123] Example 11 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by formula 2 (where R3 is 6-CH(CH5)2- (other substitution positions on the pyridine ring substituted by R3 are H), R4 is 4-Cl (other substitution positions on the pyridine ring substituted by R4 are H), and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 37 °C and maintained at a constant pressure of ethylene monomer (2.9 bar). Then, methylaluminoxane (MAO) (1.584 mol) was added to initiate ethylene polymerization. The reaction time was 14 min. The introduction of ethylene monomer was then stopped.

[0124] 1,3-Butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After complete removal of the ethylene monomer, 2.78 mol of 1,3-butadiene was added. Under a constant pressure (3 bar), diethylaluminum chloride (1.584 mol) was added to initiate the copolymerization of butadiene monomer. The copolymerization temperature was 50°C and the copolymerization time was 1 hour. A 5% toluene solution of 2,2-methylenebis(4-methyl-6-tert-butylphenol) was added as a stabilizer. Then, 20 mL of a 4% hydrochloric acid solution in methanol was added to the polymerization system to terminate the reaction. Finally, the polymerization product was dissolved by washing with methanol and toluene three times, and then vacuum dried to obtain 261.3 g of copolymer. The molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:701:701. The molar ratio of catalyst to 1,3-butadiene is 1:1230.

[0125] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The resulting spectrogram, as shown in Figure 4, shows the characteristic peaks of butadiene rubber at wavenumbers 1647 and 731, and the characteristic peak of the polyethylene segment at wavenumber 720.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The resulting spectrogram shows the butadiene rubber peak at chemical shift 5.4 and the ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 68.7 wt%, and the butadiene rubber segment content is 31.3 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 92.5 mol%, the trans 1,4-structure content is 4.7 mol%, and the 1,2-structure content is 2.8 mol%.

[0126] DSC test data: As can be seen from Figure 3, the copolymer has a Tg of -110.6°C, a Tm of 134.4°C, a Tc of 115.1°C, a crystallinity of 56.0%, and a length of consecutive methylene sequences of 278 to 456. GPC test data: The copolymer has a number average molecular weight of 183,000 g / mol and a molecular weight distribution of 5.75.

[0127] Example 12 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 3 (where R5 is 4-CH3- (other substituents on the dihydrooxazole ring are H), R6 is H (other substituents on the pyridine ring are H), and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 32 °C and maintained at a constant pressure (4 bar) of ethylene monomer. Then, methylaluminoxane (MAO) (0.452 mol) was added to initiate ethylene polymerization. The introduction of ethylene monomer was stopped after the reaction time reached 20 min.

[0128] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 3.52 mol of 1,3-butadiene was added. A constant pressure (3.2 bar) was maintained, and diethylaluminum chloride (0.678 mol) was injected to initiate the continuous polymerization of butadiene monomer. The copolymerization temperature was 48°C, and the copolymerization time was 1 hour. The molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:200:300. The molar ratio of catalyst:1,3-butadiene was 1:1558.

[0129] The polymerization product was post-treated according to the method of Example 11 to obtain 391.1 g of copolymer.

[0130] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1648 and 741, and a characteristic peak of a polyethylene segment at wavenumber 721.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 64.1 wt%, and the butadiene rubber segment content is 35.9 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 92.7 mol%, the trans 1,4-structure content is 4.6 mol%, and the 1,2-structure content is 2.7 mol%.

[0131] The DSC test data show that the copolymer has a Tg of -102.4°C, a Tm of 140.2°C, a Tc of 117.8°C, a crystallinity of 51.9%, and a length of consecutive methylene sequences of 645 to 1060. GPC test data show that the copolymer has a number average molecular weight of 258,000 g / mol and a molecular weight distribution of 5.68.

[0132] Example 13 (1) After cycling the polymerization reactor three times using the Schlenk method, 3 L of toluene, ethylene, and the catalyst represented by Formula 3 (where R5 is 4-CH2CH3- (other substituents on the dihydrooxazole ring are H), R6 is 4-CH3- (other substituents on the pyridine ring are H), and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 42 °C, and ethylene monomer was introduced to maintain a constant pressure (9 bar). After this, methylaluminoxane (MAO) (1.584 mol) was added to initiate ethylene polymerization. After 20 min of ethylene polymerization, the introduction of ethylene monomer was stopped.

[0133] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 7.56 mol of 1,3-butadiene was added. A constant pressure (2.5 bar) atmosphere was maintained, and diisobutylaluminum chloride (1.584 mol) was injected to initiate the copolymerization of butadiene. The copolymerization temperature was 45°C, and the copolymerization time was 1.6 h. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:701:3345, and the molar ratio of catalyst:1,3-butadiene was 1:3345.

[0134] The polymerization product was post-treated according to the method of Example 11 to obtain 491.9 g of copolymer.

[0135] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 738, and a characteristic peak of a polyethylene segment at wavenumber 721.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 37.9 wt%, and the butadiene rubber segment content is 62.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 94.0 mol%, the trans 1,4-structure content is 3.7 mol%, and the 1,2-structure content is 2.3 mol%.

[0136] The DSC test data show that the copolymer has a Tg of -109.9°C, a Tm of 136.3°C, a Tc of 115.9°C, a crystallinity of 29.6%, and a length of consecutive methylene sequences of 342 to 563. GPC test data show that the copolymer has a number average molecular weight of 320,000 g / mol and a molecular weight distribution of 4.45.

[0137] Example 14 (1) After cycling the polymerization reactor three times using the Schlenk method, 4 L of toluene, ethylene, and 2.260 mmol of the catalyst represented by formula 3 (where R5 is 4-CH(CH3)2- (other substituents on the dihydrooxazole ring are H), R6 is 4-OCH3- (other substituents on the pyridine ring are H), and X is chlorine) were added to the polymerization reactor and stirred at high speed using a mechanical stirrer to homogeneously disperse the mixture. The homogeneously dispersed mixture was heated to 50 °C, and ethylene monomer was introduced to maintain a constant pressure (40 bar). Then, methylaluminoxane (MAO) (0.904 mol) was added to initiate ethylene polymerization. The introduction of ethylene monomer was stopped after the reaction time reached 18 min.

[0138] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 2.78 mol of 1,3-butadiene was added. Under a constant pressure (4.2 bar), sesquiethylaluminum (0.904 mmol) was added to initiate the copolymerization of butadiene. The copolymerization temperature was 45°C and the copolymerization time was 1 hour. The molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:400:400, and the molar ratio of catalyst:1,3-butadiene was 1:1230.

[0139] The polymerization product was post-treated according to the method of Example 11 to obtain 431.5 g of copolymer.

[0140] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1649 and 733, and a characteristic peak of a polyethylene segment at wavenumber 722.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 72.9 wt%, and the butadiene rubber segment content is 27.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 92.0 mol%, the trans 1,4-structure content is 5.1 mol%, and the 1,2-structure content is 2.9 mol%.

[0141] The DSC test data show that the copolymer has a Tg of -101.7°C, a Tm of 142.1°C, a Tc of 120.9°C, a crystallinity of 59.8%, and a length of consecutive methylene sequences of 922 to 1,800. GPC test data show that the copolymer has a number average molecular weight of 303,000 g / mol and a molecular weight distribution of 5.98.

[0142] Example 15 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by formula 3 (where R5 is 4-CH5- (other substituents on the dihydrooxazole ring are H), R6 is 4-CF3- (other substituents on the pyridine ring are H), and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 45 °C, ethylene monomer was introduced, and a constant pressure (4 bar) was maintained. Then, methylaluminoxane (MAO) (1.131 mol) was added to initiate ethylene polymerization. The reaction time was 7 min. The introduction of ethylene monomer was then stopped.

[0143] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 16.8 mol of 1,3-butadiene was added. Under a constant pressure (4.5 bar), sesquiethylaluminum (1.131 mol) was added to initiate the copolymerization of butadiene. The copolymerization temperature was 40°C and the copolymerization time was 4 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:500:500, and the molar ratio of catalyst:1,3-butadiene was 1:7434.

[0144] The polymerization product was post-treated according to the method of Example 11 to obtain 847.9 g of copolymer.

[0145] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1646 and 738, and a characteristic peak of a polyethylene segment at wavenumber 721.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 4.2 wt%, and the butadiene rubber segment content is 95.8 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 97.5 mol%, the trans 1,4-structure content is 1.5 mol%, and the 1,2-structure content is 1.0 mol%.

[0146] The DSC test data show that the copolymer has a Tg of -111.7°C, a Tm of 128.1°C, a Tc of 108.9°C, a crystallinity of 3.0%, and a length of consecutive methylene sequences of 170 to 278. GPC test data: The copolymer has a number average molecular weight of 586,000 g / mol and a molecular weight distribution of 2.97.

[0147] Example 16 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH3- (other substituents on the benzene ring are H), R2 is H (all substituents on the pyridine ring are H), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 38 °C and maintained at a constant pressure (4 bar) of ethylene monomer. Then, methylaluminoxane (MAO) (1.584 mol) was added to initiate ethylene polymerization. The introduction of ethylene monomer was stopped after the reaction time reached 20 min.

[0148] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 9.02 mol of 1,3-butadiene was added. A constant pressure (2.8 bar) was maintained, and diisobutylaluminum chloride (1.584 mol) was added to initiate the copolymerization of butadiene. The copolymerization temperature was 45°C, and the copolymerization time was 3 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:701:701, and the molar ratio of catalyst:1,3-butadiene was 1:3991.

[0149] The polymerization product was post-treated according to the method of Example 11 to obtain 496.4 g of copolymer.

[0150] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 738, and a characteristic peak of a polyethylene segment at wavenumber 721.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 21.1 wt%, and the butadiene rubber segment content is 79.9 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 95.0 mol%, the trans 1,4-structure content is 3.1 mol%, and the 1,2-structure content is 1.9 mol%.

[0151] The DSC test data of the in-situ reinforced butadiene rubber shows Tg = -108.9°C, Tm = 135.2°C, Tc = 113.9°C, a crystallinity of 16.0%, and a length of consecutive methylene sequences of 302 to 496. GPC test data: The copolymer has a number average molecular weight of 338,000 g / mol and a molecular weight distribution of 3.83.

[0152] Example 17 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH2CH3- (other substituents on the benzene ring are H), R2 is H (all substituents on the pyridine ring are H), R7 is methyl, and X is bromine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 45 °C, ethylene monomer was introduced, and a constant pressure (4 bar) was maintained. Then, methylaluminoxane (MAO) (2.034 mol) was added to initiate ethylene polymerization. The introduction of ethylene monomer was stopped after the reaction time reached 20 min.

[0153] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 8.57 mol of 1,3-butadiene was added. A constant pressure (4 bar) atmosphere was maintained, and diisobutylaluminum chloride (2.034 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 43°C, and the copolymerization reaction time was 3 hours. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:900:900. The molar ratio of catalyst:1,3-butadiene was 1:3792.

[0154] The polymerization product was post-treated according to the method of Example 11 to obtain 377.9 g of copolymer.

[0155] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 741, and a characteristic peak of a polyethylene segment at wavenumber 722.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 18.5 wt%, and the butadiene rubber segment content is 81.5 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 95.3 mol%, the trans 1,4-structure content is 3.0 mol%, and the 1,2-structure content is 1.7 mol%.

[0156] The DSC test data show that the copolymer has a Tg of -107.9°C, a Tm of 134.5°C, a Tc of 112.5°C, a crystallinity of 14.0%, and a length of consecutive methylene sequences of 278 to 465. GPC test data show that the copolymer has a number average molecular weight of 256,000 g / mol and a molecular weight distribution of 3.76.

[0157] Example 18 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH(CH3)2- (other substituents on the benzene ring are H), R2 is 4-Cl (other substituents on the pyridine ring are H), R7 is methyl, and X is bromine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 36 °C, ethylene monomer was introduced, and a constant pressure (4 bar) was maintained. Diethylaluminum chloride (226 mmol) was then added to initiate ethylene polymerization. After the reaction time reached 20 min, the introduction of ethylene monomer was stopped.

[0158] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 9.39 mol of 1,3-butadiene was added. A constant pressure (3.3 bar) was maintained, and diisobutylaluminum chloride (1.584 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 47°C, and the copolymerization reaction time was 3 hours. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:100:701. The molar ratio of catalyst: 1,3-butadiene was 1:4155.

[0159] The polymerization product was post-treated according to the method of Example 11 to obtain 467.1 g of copolymer.

[0160] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1), (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1637 and 731, and a characteristic peak of a polyethylene segment at wavenumber 720.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 7.9 wt%, and the butadiene rubber segment content is 92.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 96.6 mol%, the trans 1,4-structure content is 2.0 mol%, and the 1,2-structure content is 1.4 mol%.

[0161] The DSC test data show that the copolymer has a Tg of -105.9°C, a Tm of 135.1°C, a Tc of 115.9°C, a crystallinity of 5.8%, and a length of consecutive methylene sequences of 295 to 493. GPC test data show that the copolymer has a number average molecular weight of 318,000 g / mol and a molecular weight distribution of 3.08.

[0162] Example 19 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,4,6-CH3- (other substituents on the benzene ring are H), R2 is H (all substitutions on the pyridine ring are H), R7 is all methyl, and X is bromine) (2.260 mmol) were added to the polymerization reactor, and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 43 °C, ethylene monomer was introduced, and a constant pressure (5.9 bar) was maintained. Then, methylaluminoxane (MAO) (0.678 mol) was added to initiate ethylene polymerization. The introduction of ethylene monomer was stopped after the reaction time reached 20 min.

[0163] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 10.7 mol of 1,3-butadiene was added. A constant pressure (3.8 bar) was maintained, and diisobutylaluminum chloride (0.339 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 48°C, and the copolymerization reaction time was 3 hours. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:300:150. The molar ratio of catalyst: 1,3-butadiene was 1:4735.

[0164] The polymerization product was post-treated according to the method of Example 1 to obtain 531.7 g of copolymer.

[0165] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ), (The spectrogram shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 741, and a characteristic peak of a polyethylene segment at wavenumber 721.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 9.9 wt%, and the butadiene rubber segment content is 90.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 96.2 mol%, the trans 1,4-structure content is 2.3 mol%, and the 1,2-structure content is 1.5 mol%.

[0166] The DSC test data show that the copolymer has a Tg of -110.8°C, a Tm of 135.2°C, a Tc of 117.9°C, a crystallinity of 7.4%, and a length of consecutive methylene sequences of 297 to 502. GPC test data show that the copolymer has a number average molecular weight of 373,000 g / mol and a molecular weight distribution of 3.28.

[0167] Example 20 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH5- (other substituents on the benzene ring are H), R2 is H (all substitution positions on the pyridine ring are H), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 51 °C, ethylene monomer was introduced, and a constant pressure (2.7 bar) was maintained. Modified methylaluminoxane (MMAO) (1.584 mol) was then added to initiate ethylene polymerization. After 20 min of ethylene polymerization, the introduction of ethylene monomer was stopped.

[0168] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 4.94 mol of 1,3-butadiene was added. A constant pressure (4 bar) atmosphere was maintained, and diisobutylaluminum chloride (1.584 mol) was injected to convert the active center and initiate the polymerization reaction of butadiene monomer. The copolymerization temperature was 51°C, and the copolymerization time was 3 h. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:701:701. The molar ratio of catalyst: 1,3-butadiene was 1:2186.

[0169] The polymerization product was post-treated according to the method of Example 11 to obtain 247.1 g of copolymer.

[0170] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1), (The spectrogram shows characteristic peaks of butadiene rubber at wavenumbers 1644 and 739, and a characteristic peak of a polyethylene segment at wavenumber 720.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 24.9 wt%, and the butadiene rubber segment content is 75.1 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 94.7 mol%, the trans 1,4-structure content is 3.2 mol%, and the 1,2-structure content is 2.1 mol%.

[0171] The DSC test data show that the copolymer has a Tg of -105.3°C, a Tm of 136.7°C, a Tc of 114.8°C, a crystallinity of 19.0%, and a length of consecutive methylene sequences of 358 to 595. GPC test data show that the copolymer has a number average molecular weight of 166,000 g / mol and a molecular weight distribution of 3.91.

[0172] Comparative Example 1 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene and 2.260 mmol of the catalyst represented by Formula 1 (where R1 = 2,4,6-CH3- (other substituents on the benzene ring are H), R2 = H (all substitution positions on the pyridine ring are H), R7 = methyl, and X = bromine) were added to the polymerization reactor and the mixture was stirred at high speed using a mechanical stirrer to homogeneously disperse the mixture. The homogeneously dispersed mixture was heated to 70 °C, and 3.87 mol of 1,3-butadiene was added. Under a constant pressure (3 bar), diisobutylaluminum chloride (1.584 mol) was added to initiate the polymerization of butadiene monomer. The reaction time was 4 h. The molar ratio of catalyst to chloroaluminum-containing cocatalyst-2 was 1:701. The molar ratio of catalyst to 1,3-butadiene was 1:1712.

[0173] The polymerization product was post-treated according to the method of Example 11 to obtain 189.7 g of butadiene rubber.

[0174] (2) Appearance of the obtained butadiene rubber: FT-IR (KBr, cm -1 ), (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers of 1644 and 739; nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at a chemical shift of 5.4; The butadiene rubber segment content is 100.0 wt%, the cis 1,4-structure content is 98.2 mol%, the trans 1,4-structure content is 1.2 mol%, and the 1,2-structure content is 0.6 mol%.

[0175] DSC test data shows that the butadiene rubber has a Tg of -109.5°C. GPC test data: the copolymer has a number average molecular weight of 129,000 g / mol and a molecular weight distribution of 2.68.

[0176] Comparative Example 2 The butadiene rubber prepared in Comparative Example 1 was blended with the polyethylene solution to prepare 124.6 g of a blend with a polyethylene content of 8.2% (compared to Example 4).

[0177] As can be seen from the DSC test data, the blend has Tg=-108.1°C, Tm=138.7°C, Tc=121.5°C, and a crystallinity of 5.5%.

[0178] Comparative Example 3 The butadiene rubber prepared in Comparative Example 1 was blended with the polyethylene solution to prepare 100.6 g of a blend with a polyethylene content of 12.9% (compared to Example 6).

[0179] As can be seen from the DSC test data, the blend has a Tg of -107.5°C, a Tm of 140.7°C, a Tc of 121.7°C, and a crystallinity of 9.0%.

[0180] Comparative Example 4 The butadiene rubber prepared in Comparative Example 1 was blended with the polyethylene solution to prepare 85.6 g of a blend with a polyethylene content of 4.9% (compared to Example 7).

[0181] As can be seen from the DSC test data, the blend has Tg=-107.0°C, Tm=139.2°C, Tc=121.0°C, and a crystallinity of 2.9%.

[0182] Comparative Example 5 (1) After three cycles of Schlenk circulation in the polymerization reactor, 2 L of toluene and 2.260 mmol of the catalyst (Eq. 1) (where R1 = 2,6-CH(CH3)2- (all other substituents on the benzene ring are H), R2 = H (all substitutions on the pyridine ring are H), R7 = methyl, and X = chlorine) were added to the polymerization reactor and stirred at high speed with a mechanical stirrer to homogeneously disperse the mixture. The homogeneously dispersed mixture was heated to 45 °C, and diisobutylaluminum chloride (0.679 mol) and methylaluminoxane (MAO) (0.679 mol) were added. 5.56 mol of 1,3-butadiene was added. Ethylene monomer was introduced to maintain a constant pressure (10 bar). The copolymerization temperature was raised to 40 °C. After 10 min of polymerization, the introduction of ethylene monomer was stopped, and the reaction time was 3 h. Here, the molar ratio of catalyst:aluminum-containing cocatalyst-1:chloroaluminum-containing cocatalyst-2 was 1:300:300, and the molar ratio of catalyst:1,3-butadiene was 1:2460.

[0183] The polymerization product was post-treated according to the method of Example 1 to obtain 268.4 g of copolymer.

[0184] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1), (The spectrogram shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 741, and a characteristic peak of polyethylene at wavenumber 721.); Conversion based on nuclear magnetic resonance hydrogen spectrum: The content of ethylene structural units is 6.7 wt%, the content of butadiene structural units is 93.3 wt%, and in the butadiene structural units, the content of cis 1,4-structures is 85.8 mol%, the content of trans 1,4-structures is 8.7 mol%, and the content of 1,2-structures is 5.5 mol%.

[0185] DSC test data shows that the copolymer has a Tg of -106.7°C, and no obvious crystals were observed. GPC test data: the copolymer has a number average molecular weight of 68,000 g / mol and a molecular weight distribution of 3.22.

[0186] Comparative Example 6 (1) After three cycles of Schlenk circulation in the polymerization reactor, 2 L of toluene and 2.260 mmol of the catalyst represented by Formula 1 (where R1 = 2,4,6-CH3- (other substituents on the benzene ring are H), R2 = H (all substitution positions on the pyridine ring are H), R7 = methyl, and X = bromine) were added to the polymerization reactor. The mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 70 °C, 8.8 mol of 1,3-butadiene was added, and diisobutylaluminum chloride (1.584 mol) was added under a constant pressure (3 bar) to initiate the polymerization of butadiene monomer. The reaction time was 4 h. A 5% toluene solution of 2,2-methylenebis-(4-methyl-6-tert-butylphenol) was added as a stabilizer, and then 20 mL of a 4% hydrochloric acid solution in methanol was added to the polymerization system to terminate the reaction. Here, the molar ratio of catalyst to chloroaluminum-containing cocatalyst-2 is 1:701, and the molar ratio of catalyst to 1,3-butadiene is 1:3894.

[0187] (2) After the polymerization reactor was cycled three times by the Schlenk method, 2 L of toluene and the catalyst represented by Formula 1 (wherein R1 is 2,6-CH2CH3- (other substitution positions on the benzene ring are H), R2 is 4-N(CH3)2- (other substitution positions on the pyridine ring are H), R7 is phenyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor, and the mixture was stirred at high speed by mechanical stirring to uniformly disperse the mixture. The homogeneously dispersed mixture was heated to 33°C, ethylene monomer was introduced, and a constant pressure (5 bar) atmosphere was maintained. Modified methylaluminoxane (MMAO) (1.584 mol) was then added to initiate ethylene polymerization. The reaction time was 18 min. A 5% toluene solution of 2,2-methylenebis-(4-methyl-6-tert-butylphenol) was added as a stabilizer. Next, 20 mL of a 4% hydrochloric acid solution in methanol was added to the polymerization system to terminate the reaction, which was synchronized with the reaction in step (1). The molar ratio of catalyst to aluminum-containing cocatalyst-1 was 1:701.

[0188] (3) The solutions from step (1) and step (2) were mechanically stirred at high speed to uniformly mix the two, and the polymerization product was post-treated according to the method of Example 11 to obtain 474.4 g of a blend. The polyethylene segment content was 8.2 wt%, and the butadiene rubber segment content was 91.8 wt%. In the butadiene rubber segment, the cis 1,4-structure content was 98.2 mol%, the trans 1,4-structure content was 1.1 mol%, and the 1,2-structure content was 0.7 mol%.

[0189] As can be seen from the DSC test data, the blend has Tg=-109.5°C, Tm=138.8°C, Tc=121.3°C, and a crystallinity of 5.7%.

[0190] Comparative Example 7 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is 2,6-CH(CH3)2- (other substituents on the benzene ring are H), R2 is 4-OCH3- (other substituents on the pyridine ring are H), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 39 °C and maintained at a constant pressure of ethylene monomer (4.9 bar). Then, methylaluminoxane (MAO) (1.36 mol) was added to initiate the polymerization of ethylene. After 55 s of polymerization, the introduction of ethylene monomer was stopped.

[0191] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 3.24 mol of 1,3-butadiene was added. A constant pressure (2 bar) atmosphere was maintained, and diisobutylaluminum chloride (0.679 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 48°C, and the copolymerization reaction time was 4 hours. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:602:300. The molar ratio of catalyst: 1,3-butadiene was 1:1433.

[0192] The polymerization product was post-treated according to the method of Example 1 to obtain 166.7 g of copolymer.

[0193] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1644 and 734, and a characteristic peak of a polyethylene segment at wavenumber 719.); Nuclear magnetic resonance hydrogen spectrum (ppm) (The spectrogram obtained shows a butadiene rubber peak at chemical shift 5.4 and an ethylene segment peak at chemical shift 1.10.); The polyethylene segment content is 1.8 wt%, and the butadiene rubber segment content is 98.2 wt%. In the butadiene rubber segment, the cis 1,4-structure content is 98.0 mol%, the trans 1,4-structure content is 1.2 mol%, and the 1,2-structure content is 0.8 mol%.

[0194] The DSC test data show that the copolymer has a Tg of -111.7°C, a Tm of 108.5°C, a Tc of 95.4°C, a crystallinity of 0.7%, and a length of consecutive methylene sequences of 45 to 124. GPC test data show that the copolymer has a number average molecular weight of 142,000 g / mol and a molecular weight distribution of 2.74.

[0195] Comparative Example 8 (1) After cycling the polymerization reactor three times using the Schlenk method, 2 L of toluene, ethylene, and the catalyst represented by Formula 1 (where R1 is H (all other substituents on the benzene ring are H), R2 is H (all substituents on the pyridine ring are H), R7 is methyl, and X is chlorine) (2.260 mmol) were added to the polymerization reactor and the mixture was uniformly dispersed by high-speed mechanical stirring. The uniformly dispersed mixture was heated to 30 °C and maintained at a constant pressure (4 bar) of ethylene monomer. Then, methylaluminoxane (MAO) (0.679 mol) was added to initiate the polymerization of ethylene. After 5 min of polymerization, the introduction of ethylene monomer was stopped.

[0196] 1,3-butadiene monomer was introduced into the polymerization reactor, and unpolymerized ethylene monomer was purged. After the ethylene monomer was completely removed, 5.56 mol of 1,3-butadiene was added. A constant pressure (3 bar) atmosphere was maintained, and diisobutylaluminum chloride (0.679 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 45°C, and the copolymerization reaction time was 2 hours. Here, the molar ratio of catalyst: aluminum-containing cocatalyst-1: chloroaluminum-containing cocatalyst-2 was 1:300:300. The molar ratio of catalyst: 1,3-butadiene was 1:2460.

[0197] The polymerization product was post-treated according to the method of Example 1 to obtain 251.6 g of copolymer.

[0198] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ) (The spectrogram obtained shows characteristic peaks of butadiene rubber at wavenumbers 1647 and 741, and a characteristic peak of polyethylene at wavenumber 722.); Nuclear magnetic resonance hydrogen spectrum: The content of ethylene structural units is 0.2 wt%, the content of butadiene structural units is 99.8 wt%, and in the butadiene structural units, the content of cis 1,4-structures is 98.2 mol%, the content of trans 1,4-structures is 1.1 mol%, and the content of 1,2-structures is 0.7 mol%.

[0199] DSC test data shows that the copolymer has a Tg of -110.9°C and no obvious crystals were observed. GPC test data: the copolymer has a number average molecular weight of 317,000 g / mol and a molecular weight distribution of 2.84.

[0200] The breaking strength of the vulcanized rubbers obtained in the examples and comparative examples was measured by the following method.

[0201] Compounding and vulcanization: The copolymers prepared in the examples and the butadiene rubbers and blends provided in the comparative examples were each prepared into vulcanized rubber samples by the following method.

[0202] Mixing process: All vulcanized rubber compositions were mixed using a Hapro RM-200A torque rheometer (Harbin Hapro Electric Technology Co., Ltd.), and the mixed samples were passed through a two-roll mill 20 times to obtain the final mixed rubber. The mixing conditions are shown in Table 1.

[0203] Preparation of vulcanized rubber sample: The obtained kneaded rubber was left at room temperature for 24 hours, then placed on a processing template and vulcanized in an XLB-D350×350 flat plate vulcanizer with the vulcanization temperature set to 150°C and the vulcanization time set to t90.

[0204] [Table 1]

[0205] The prepared vulcanized rubber samples were measured according to standard GB / T 528-1998 to obtain the breaking strength of the vulcanized rubber, and according to standard GB / T 529-1999 to obtain the tear strength of the vulcanized rubber, and the results are shown in Table 2.

[0206] [Table 2]

[0207] [Table 3]

[0208] [Table 4]

[0209] [Table 5]

[0210] [Table 6]

[0211] [Table 7]

[0212] The results in Table 2 and a comparison with the comparative examples show that the copolymers prepared by the single-stage polymerization method of the present invention in the examples have superior reinforcing properties and higher breaking strength and tear strength of the vulcanized rubber. Tm tends to increase with increasing polyethylene content, and the length of consecutive methylene sequences also increases with increasing Tm. Compared with comparative examples 2 to 4 and 6, polymers with the same ethylene content have lower Tm and tend to improve in crystallinity with increasing polyethylene content, and the breaking strength and tear strength of the vulcanized rubber also tend to improve with increasing crystallinity. Compared with comparative examples 2 to 4 and 6, polymers with the same ethylene content have higher crystallinity and higher breaking strength and tear strength. With increasing polyethylene content, the content of cis-1,4-structures in the polybutadiene segments in the copolymers decreases slightly, and with increasing molecular weight of the polymer, the strength of the vulcanized rubber also tends to improve. With increasing polyethylene content, the molecular weight distribution tends to increase. In Comparative Example 5, the polymer obtained had a low molecular weight, a reduced cis-1,4 content, and no crystallization of the ethylene segments, resulting in low breaking strength and tear strength of the vulcanized rubber. The copolymer obtained in Comparative Example 7 had a relatively short methylene sequence length, resulting in lower mechanical strength of the vulcanized rubber compared to Examples 2 and 3, which had a low ethylene content. The catalyst used in Comparative Example 8 had low steric hindrance, resulting in a relatively low ethylene content in the resulting copolymer. Therefore, polyethylene segments with relatively long methylene sequences could not be formed, resulting in poor mechanical properties of the vulcanized rubber.

[0213] Figure 6 shows TEM images of the copolymers prepared in Comparative Example 6 (left) and Example 6 (right). Figure 6 shows that the polyethylene and polybutadiene phases in the copolymers obtained by the "in-situ polymerization" method are more uniformly mixed than those obtained by solution blending or mechanical blending, and there is no obvious aggregation of the polyethylene phase.

[0214] Figure 7 shows the COSY spectrum of the copolymer prepared in Example 3. It is clear from Figure 7 that the ethylene segments are chemically bonded directly to the butadiene segments, and when the lengths of the consecutive methylene sequences are adjusted, it is clear that an ethylene-butadiene block copolymer has been formed.

[0215] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical idea of ​​the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining various technical features in other appropriate ways. These simple modifications and combinations are also considered to be the contents disclosed by the present invention and fall within the protection scope of the present invention. [Brief explanation of the drawings]

[0216] [Figure 1] 1 is a DSC chart (above room temperature) of the copolymer prepared in Example 1. [Figure 2] 1 is an infrared spectrum of the copolymer prepared in Example 1. [Figure 3] 1 is a DSC chart (above room temperature) of the copolymer prepared in Example 11. [Figure 4] 1 is an infrared spectrum of the copolymer prepared in Example 11. [Figure 5] 1 is a nuclear magnetic resonance hydrogen spectrum of the copolymer prepared in Example 6. [Figure 6] TEM of the copolymers prepared in Comparative Example 6 (left) and Example 6 (right). [Figure 7] 1 is a COSY spectrum of the copolymer prepared in Example 3.

Claims

1. A copolymer, The copolymer is a block copolymer and includes a polyethylene segment and a butadiene rubber segment, wherein a weight ratio of the polyethylene segment to the butadiene rubber segment based on the total amount of the copolymer is 0.1:99.9 to 80:20, and the butadiene rubber segment has a cis 1,4-structure content of 90 to 98.5 mol%, a trans 1,4-structural unit content of 0.9 to 5.7 mol%, and a 1,2-structural unit content of 0.6 to 4.3 mol%, based on the total amount of the butadiene rubber segment, and a length of consecutive methylene sequences in the copolymer is at least 165.

2. the weight ratio of the polyethylene segment to the butadiene rubber segment is 1:99 to 75:25; 2. The copolymer according to claim 1, wherein the length of consecutive methylene sequences in the copolymer is preferably 250 to 1,800.

3. 3. The copolymer according to claim 1, wherein the butadiene rubber segment has a cis 1,4-structure content of 92 to 98 mol % based on the total amount of the butadiene rubber segment.

4. The copolymer according to any one of claims 1 to 3, wherein the copolymer has a Tm of 120 to 150°C and a crystallinity of 0.2 to 80%, preferably a Tm of 125 to 145°C and a crystallinity of 0.5 to 65%.

5. The copolymer according to any one of claims 1 to 4, wherein the number average molecular weight is 50,000 to 800,000 g / mol and the molecular weight distribution is 2 to 7, preferably the number average molecular weight is 100,000 to 700,000 g / mol and the molecular weight distribution is 2.5 to 6.

5.

6. 1. A method for preparing a copolymer, the method comprising: Step (1): polymerizing ethylene in the presence of an organic solvent, a catalyst, and an aluminum-containing cocatalyst-1 to obtain a polyethylene product, wherein the polymerization temperature is 20-70°C, the ethylene pressure is maintained at 1-70 bar, and the polymerization time is 1-80 min; (2) introducing 1,3-butadiene monomer into the polyethylene product and removing unreacted ethylene monomer; and step (3) adding a chloroaluminum-containing cocatalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between 1,3-butadiene monomer and the polyethylene active segments in the polyethylene product, thereby obtaining the copolymer; The method for preparing a copolymer, wherein the catalyst is at least one selected from the compounds represented by formula 1, formula 2, and formula 3. 【Chemical 1】 (wherein X is chlorine or bromine, R １ are mono- or 4-substituted substituents on the benzene ring, or identical or different di-substituted substituents on the benzene ring at the 2, 4 or 2, 6-positions, or identical or different tri-substituted substituents on the benzene ring at the 2, 4, and 6-positions, wherein the substituents are -F, -CH ３ , -CH ２ CH ３ , -CH(CH ３ ) ２ , -C(CH ３ ) ３ , -C ６ H ５ , or —CH(C ６ H ５ ) ２ and R ３ is a monosubstituted —CH group at the 6-position on the pyridine ring. ３ , -CH ２ CH ３ , -CH(CH ３ ) ２ , -C(CH ３ ) ３ , -C ６ H ５ , or —CH(C ６ H ５ ) ２ or a mono-substituted —CH group at the 4-position on the pyridine ring ３ , -N(CH ３ ) ２ , or -CF ３ or the same or different —CH 2-substituted at the 4- and 6-positions on the pyridine ring ３ , -CH ２ CH ３ , -C ６ H ５ , —CH(C ６ H ５ ) ２ , -N(CH ３ ) ２ , or -CF ３ and R ５ is a monosubstituted —CH group at the 4-position on the dihydrooxazole ring. ３ , -CH ２ CH ３ , -CH(CH ３ ) ２ , -C(CH ３ ) ３ , -C ６ H ５ , or —CH(C ６ H ５ ) ２ and R ２ , R ４ , R ６ are each independently H, or —Cl, —F, or —CH monosubstituted at the 4-position on the pyridine ring. ３ , -OCH ３ , -N(CH ３ ) ２ , or -CF ３ and R ７ is H, -CH ３ , -CH ２ CH ３ , -CH(CH ３ ) ２ , -C(CH ３ ) ３ , -Cl, -C ６ H ５ , or —CH(C ６ H ５ ) ２ It is.)

7. In step (1), the polymerization temperature is 30-60°C, the ethylene pressure is maintained at 2.5-50 bar, and the polymerization time is 2-60 min; 7. The method according to claim 6, wherein the organic solvent is at least one selected from n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decalin, dodecane, hydrogenated gasoline, preferably toluene.

8. the molar ratio of the catalyst to aluminum-containing cocatalyst-1 to chloroaluminum-containing cocatalyst-2 is 1:15 to 1,000:20 to 1,000, preferably 1:20 to 900:40 to 900; The preparation method according to claim 6 or 7, wherein the chloroaluminum-containing cocatalyst-2 is preferably added in step (3).

9. The preparation method according to any one of claims 6 to 8, wherein the aluminum-containing cocatalyst-1 is at least one selected from methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-tert-butylaluminum chloride, dioctylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride, preferably at least one selected from methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, diethylaluminum chloride, di-tert-butylaluminum chloride, ethylaluminum dichloride, and sesquiethylaluminum.

10. The preparation method according to any one of claims 6 to 9, wherein the chloroaluminum-containing cocatalyst-2 is at least one selected from diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride, preferably diisobutylaluminum chloride, ethylaluminum dichloride, or sesquiethylaluminum.

11. In step (3), the concentration of 1,3-butadiene in the polymerization system obtained in step (2) is 0.4 to 12 mol / L, preferably 0.6 to 9 mol / L; Preferably, the molar ratio of the catalyst to 1,3-butadiene is 1:1,000-10,000, preferably 1:1,200-8,000; The preparation method according to any one of claims 6 to 10, wherein the temperature of the copolymerization reaction is preferably 30-70°C, preferably 40-60°C, the pressure of the copolymerization reaction is 1-10 bar, preferably 2-5 bar, and the time of the copolymerization reaction is 0.5-5 h, preferably 1-4 h.

12. A copolymer prepared by the method according to any one of claims 6 to 11.

13. A vulcanized rubber prepared from the copolymer of any one of claims 1 to 5 and 12.

14. 14. Use of the vulcanized rubber of claim 13 in tires, shoe soles, conveyor belts, hoses, or gaskets.

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