Copolymer and preparation method thereof, vulcanized rubber and application thereof

Abstract

The present invention relates to the field of butadiene rubber, and discloses a copolymer and a preparation method thereof, a vulcanized rubber and an application thereof. The copolymer comprises a polyethylene segment and a butadiene rubber segment; based on the total weight of the copolymer, the weight ratio of the polyethylene segment and the butadiene rubber segment is 0.1:99.9-80:20; in the butadiene rubber segment, based on the total amount of the butadiene rubber segment, the content of cis-1,4-structure is 90-98.5mol%. The copolymer is synthesized by in-situ polymerization, wherein the polyethylene butadiene rubber block copolymer plays a compatibilizing role, promotes the dissolution of the reinforced polyethylene phase and the butadiene rubber matrix, and a copolymer with good dispersion of reinforcing fillers can be obtained without late compounding, overcoming the problems of phase separation and interface failure in blending.

Description

Technical Field

[0001] The invention relates to the field of copolymers, and in particular to a copolymer and a preparation method thereof, a vulcanized rubber and applications thereof. Background Art

[0002] Butadiene rubber is a type of rubber material that is simply synthesized using cheap butadiene monomer as raw material. The molecular chain of butadiene rubber is regular and has no other substituent groups. Because it contains CC single bonds and a large number of free chains, the molecule is very soft. Its unique resilience, excellent wear resistance, cold resistance and dynamic performance have established its irreplaceable position in many fields such as tires, shoemaking, damping and shock absorption, and sealing industries. However, butadiene rubber also has shortcomings such as low tensile strength, tear strength and flexural strength, weak anti-slip properties, easy cold flow, and poor aging resistance, which limit its scope of application. Therefore, it is necessary to reinforce and modify butadiene rubber to overcome the shortcomings of butadiene rubber itself and expand the scope of application of butadiene rubber.

[0003] US4340685 discloses a cobalt and carbon disulfide catalyst system for in-situ synthesis of a blend of cis-1,4-polybutadiene / syndiotactic 1,2-polybutadiene and production of VCR rubber. The acidic gas generated by the use of carbon disulfide is highly corrosive to production equipment and the residue in the rubber has a certain impact on the performance.

[0004] CN105814132A discloses a method for synthesizing a polybutadiene composite material 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 catalytic systems during the polymerization process. In the first step, lanthanide catalysts are used to polymerize cis-1,4 polybutadiene, and then cobalt catalysts are used to add carbon disulfide to polymerize the cis-1,4 polybutadiene mixture to form syndiotactic 1,2-polybutadiene and thereby produce composite polybutadiene.

[0005] US9985115B2, US6291591B2 and US6331594B2 disclose the use of iron, chromium or molybdenum catalysts to polymerize butadiene in saturated alkanes of butadiene rubber to synthesize a blend of cis-1,4-polybutadiene / syndiotactic 1,2-polybutadiene.

[0006] The above in-situ generated syndiotactic 1,2-polybutadiene is compounded with butadiene rubber solution. Since butadiene rubber is used as the dispersion, the polymerization activity is insufficient, the polymerization process is difficult to control, and the composition is not easy to adjust. More importantly, the two are not compatible, and phase separation and interface problems are easily generated, which affects the material properties.

[0007] At present, in order to improve the tensile strength and tear resistance of butadiene rubber products, thereby improving the performance and service life of butadiene rubber products, it is necessary to develop new butadiene rubber reinforcement technologies. Summary of the invention

[0008] The purpose of the present invention is to improve the tensile strength and tear resistance of existing cis-1,1-diene rubber materials, and provide a copolymer and a preparation method thereof, a vulcanized rubber and an application thereof. An ethylene structure segment is introduced into the butadiene structure segment of cis-1,1-diene rubber to achieve modification of the cis-1,1-diene rubber.

[0009] The first aspect of the present invention provides a copolymer, wherein the copolymer comprises a polyethylene segment and a butadiene rubber segment; based on the total weight of the copolymer, the weight ratio of the polyethylene segment to the butadiene rubber segment is 0.1:99.9-80:20; in the butadiene rubber segment, based on the total amount of the butadiene rubber segment, the content of cis 1,4-structure is 90-98.5 mol%.

[0010] A second aspect of the present invention provides a method for preparing a copolymer, the method comprising:

[0011] (1) in the presence of an organic solvent and a catalyst, using an aluminum-containing cocatalyst-1 to initiate a polymerization reaction of ethylene monomer to obtain a polyethylene product;

[0012] (2) introducing 1,3-butadiene monomer into the polyethylene product and removing unreacted ethylene monomer;

[0013] (3) adding the aluminum-containing co-catalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between the 1,3-butadiene monomer and the polyethylene active chain segment in the polyethylene product to obtain the copolymer.

[0014] The 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 vulcanized rubber prepared from the copolymer of the present invention.

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

[0017] Through the above technical solution, the present invention has the following advantages compared with the prior art:

[0018] The present invention synthesizes a copolymer by in-situ polymerization, wherein the polyethylene butadiene rubber block copolymer plays a compatibilizing role, promotes the dissolution of the reinforcing polyethylene phase and the butadiene rubber matrix, and can obtain a copolymer with good dispersion of reinforcing fillers without the need for subsequent compounding, thereby overcoming the problems of phase separation, interface failure, etc. existing in blending.

[0019] The present invention can simultaneously synthesize two polymers, polyethylene and butadiene rubber, through a one-step polymerization process using a catalyst. Compared with a step-by-step polymerization method, the present invention has the advantages of simple process, strong operability, low cost, easier adjustment of the polymerization process and the composition of the composite material, and is conducive to industrial production.

[0020] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the DSC graph of the copolymer obtained in Example 1 (part above room temperature);

[0022] Figure 2 This is the infrared spectrum of the copolymer obtained in Example 1;

[0023] Figure 3 This is the DSC chart of the copolymer obtained in Example 11 (part above room temperature);

[0024] Figure 4 This is the infrared spectrum of the copolymer obtained in Example 11;

[0025] Figure 5 This is the H-NMR spectrum of the copolymer obtained in Example 6. DETAILED DESCRIPTION

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

[0027] The first aspect of the present invention provides a copolymer, wherein the copolymer comprises a polyethylene segment and a butadiene rubber segment; based on the total weight of the copolymer, the weight ratio of the polyethylene segment to the butadiene rubber segment is 0.1:99.9-80:20; in the butadiene rubber segment, based on the total amount of the butadiene rubber segment, the content of cis 1,4-structure is 90-98.5 mol%.

[0028] The copolymer provided by the present invention may be a polyethylene segment formed by an ethylene structural unit in addition to the cis-1,4-butadiene structural unit (the structural unit can form a cis-1,4-polybutadiene rubber segment) in cis-1,4-butadiene rubber (i.e., cis-1,4-polybutadiene rubber), to form a copolymer structure having a cis-1,4-butadiene structural unit and an ethylene structural unit, so as to achieve the modification of the cis-1,4-butadiene rubber segment and improve the shortcomings of the tensile strength and tear resistance of the existing cis-1,4-polybutadiene rubber material. In some preferred embodiments of the present invention, preferably, based on the total weight of the copolymer, the weight ratio of the polyethylene segment to the cis-1,4-butadiene rubber segment is 1:99-75:25.

[0029] The copolymer provided by the present invention may contain a structure obtained by 1,4 addition polymerization or a structure obtained by 1,2 polymerization in the cis-1,4-butadiene rubber segment, providing the copolymer with improved performance. In some preferred embodiments, preferably, in the cis-1,4-butadiene rubber segment, based on the total amount of the cis-1,4-butadiene rubber segment, the content of the cis-1,4-structure is 92-98 mol%.

[0030] The copolymer provided by the present invention has the above structure. In some preferred embodiments, preferably, the Tm of the copolymer is 120-150°C, and the crystallinity is 0.2-80%; preferably, the Tm is 125-145°C, and the crystallinity is 0.5-65%. The above properties of the copolymer can be measured by DSC method.

[0031] The copolymer provided by the present invention preferably has a number average molecular weight of 50,000-800,000 g / mol and a molecular weight distribution of 2-7; preferably, a number average molecular weight of 100,000-700,000 g / mol and a distribution of 2.5-6.5. The above properties of the copolymer can be determined by GPC method.

[0032] A second aspect of the present invention provides a method for preparing a copolymer, the method comprising:

[0033] (1) in the presence of an organic solvent and a catalyst, using an aluminum-containing cocatalyst-1 to initiate a polymerization reaction of ethylene monomer to obtain a polyethylene product;

[0034] (2) introducing 1,3-butadiene monomer into the polyethylene product and removing unreacted ethylene monomer;

[0035] (3) adding the aluminum-containing co-catalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between the 1,3-butadiene monomer and the polyethylene active chain segment in the polyethylene product to obtain the copolymer.

[0036] In the present invention, a copolymerization reaction of polyethylene and 1,3-butadiene monomer is carried out, so that in the obtained product polymer, the chain segments of polyethylene and polybutadiene are chemically bonded together to form modified butadiene rubber, thereby improving the performance of butadiene rubber.

[0037] In some embodiments of the present invention, ethylene polymerization can be carried out first, and then the copolymerization of polyethylene and 1,3-butadiene monomer can be carried out. The two reaction processes can be carried out continuously, and the same catalyst can be used in the polymerization reaction and the copolymerization reaction, and then different monomers are respectively initiated with different co-catalysts to achieve different monomer reactions to synthesize corresponding segments. Preferably, in the above method provided by the present invention, the catalytic system comprises: a catalyst, an aluminum-containing co-catalyst 1, an aluminum-containing co-catalyst 2 and an organic solvent. Wherein, the catalyst is a cobalt-based catalyst containing a cobalt organic compound. Preferably, in step (1), the catalyst is a compound of the structure shown in Formula 1 or Formula 2 or Formula 3:

[0038]

[0039] Wherein X is chlorine or bromine;

[0040] R 1 is H, or a monosubstituted substituent at position 2 or 4 on the benzene ring, or the same or different substituents at positions 2, 4 or 2, 6 on the benzene ring, or the same or different substituents at positions 2, 4, 6 on the benzene ring, wherein the substituent is -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 ;

[0041] R 3 H, or a monosubstituted -CH on the 6-position of 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 monosubstituted -CH 3、-N(CH 3 ) 2 or -CF 3 , or the same or different -CH disubstituted on the 4 and 6 positions of 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 ;

[0042] R 5 H, or a monosubstituted -CH on the 4-position of 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 ;

[0043] R 2 , R 4 , R 6 Each is independently H, or -Cl, -F, -CH monosubstituted at the 4-position of the pyridine ring 3 、-OCH 3 、-N(CH 3 ) 2 or -CF 3 .

[0044] R 7 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 .

[0045] In some embodiments of the present invention, R 1 The substituents on the benzene ring in formula 1 are allowed to be all H, preferably R1 is H; or R 1 It means that some of the substitution positions on the benzene ring are substituted groups other than H. As mentioned above, the 2nd or 4th position on the benzene ring is monosubstituted, or the 2nd, 4th or 2nd, 6th positions on the benzene ring are disubstituted, or the 2nd, 4th, 6th positions on the benzene ring are trisubstituted, and the other substitution positions are H. In the case of disubstituted and trisubstituted, the substituents may be the same or different. Preferably, the 2nd or 4th position on the benzene ring is monosubstituted with -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 , or disubstituted -F, -CH on the 2, 4 or 2, 6 positions of the benzene 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 trisubstituted -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 , more specifically, one of the following groups represented by the substitution position on the benzene ring: 2-F-, 2-CH 3 -, 4-F-, 4-CH 3 -、2,4-F-、2,4-CH 3 -, 2,6-F-, 2,6-CH 3 -、2,4,6-F-、2,4,6-CH 3 -、2-CH 2 CH 3 -、4-CH 2 CH 3 -、2,4-CH2 CH 3 -、2-CH 2 CH 3 -4-CH 3 -、2,6-CH 2 CH 3 -、2-CH 2 CH 3 -6-CH 3 -、2,4,6-CH 2 CH 3 -、2-CH(CH 3 ) 2 -、4-CH(CH 3 ) 2 -、2,4-CH(CH 3 ) 2 -、2,6-CH(CH 3 ) 2 -、2,4,6-CH(CH 3 ) 2 -、2-C(CH 3 ) 3 -、4-C(CH 3 ) 3 -、2,4-C(CH 3 ) 3 -、2,6-C(CH 3 ) 3 -、2-C(CH 3 ) 3 -6-CH 3 -、2,4,6-C(CH 3 ) 3 -、2-C 6 H 5 -、4-C 6 H 5 -、2,4-C 6 H 5 -、2,6-C 6 H 5 -、2,4,6-C 6 H 5 -、2-CH(C 6 H 5 ) 2 -、4-CH(C 6 H 5 ) 2 -、2,4-CH(C 6 H 5 ) 2 -、2,6-CH(C 6 H 5 ) 2-、2,4,6-CH(C 6 H 5 ) 2 -.

[0046] In some embodiments of the present invention, R 3 The pyridine ring in formula 2 (different from R 4 The substituents on the substituted pyridine ring) allow multiple substitution positions on the pyridine ring to be all H, preferably R 3 is H; or R 3 It means that part of the substituted positions on the pyridine ring are substituted groups other than H. As mentioned above, the 4- or 6-position on the pyridine ring is monosubstituted, or the 4- and 6-position on the pyridine ring is disubstituted, and the substituted position is H. In the case of disubstituted, the substituents may be the same or different. Preferably, the 6-position on the pyridine ring is monosubstituted with -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 , or a monosubstituted -CH 3 、-N(CH 3 ) 2 or -CF 3 , or disubstituted -CH on the 4- and 6-positions of 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 , more specifically, one of the following groups represented by the substitution position on the pyridine ring: 6-CH 3 -、6-CH 2 CH 3 -、6-C 6 H 5 -、6-CH(C 6 H 5 ) 2 -、4-CH 3 -、4-N(CH 3 ) 2 -、4-CF 3 -、4,6-CH 3-、4-CH 3 -6-CH 2 CH 3 -、4-CH 3 -6-C 6 H 5 -、4-CH 3 -6-CH(C 6 H 5 ) 2 -、4-N(CH 3 ) 2 -6-CH 3 -、4-N(CH 3 ) 2 -6-CH 2 CH 3 -、4-N(CH 3 ) 2 -6-C 6 H 5 -、4-N(CH 3 ) 2 -6-CH(C 6 H 5 ) 2 -、4-CF 3 -6-CH 3 -、4-CF 3 -6-CH 2 CH 3 -、4-CF 3 -6-C 6 H 5 -、4-CF 3 -6-CH(C 6 H 5 ) 2 -.

[0047] In some embodiments of the present invention, R 5 represents the substituents on the dihydrooxazole ring in formula 3, and multiple substitution positions on the dihydrooxazole ring are allowed to be all H, preferably R 5 is H; or R 5 It means that some of the substitution positions on the dihydrooxazole ring are substitution groups other than H. As mentioned above, the 4-position on the dihydrooxazole ring is monosubstituted, and the other substitution positions are H. Preferably, the 4-position on the dihydrooxazole ring is monosubstituted with -CH 3 、-CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 , -C 6 H 5 or -CH(C 6 H5 ) 2 , more specifically, one of the following groups represented by the substitution position on the dihydrooxazole ring: 4-CH 3 -、4-CH 2 CH 3 -、4-CH(CH 3 ) 2 -、4-C(CH 3 ) 3 -、4-C 6 H 5 -、4-CH(C 6 H 5 ) 2 -.

[0048] In some embodiments of the present invention, R 2 , R 4 , R 6 Respectively represent the substituents on the pyridine ring in Formula 1, 2, and 3 (different from R in Formula 2 3 substituted pyridine ring), allowing R 2 , R 4 , R 6 The multiple substitution positions on the substituted pyridine ring are all H, preferably R 2 , R 4 , R 6 respectively H; or, R 2 , R 4 , R 6 Respectively represent -Cl, -F, -CH substituted on the 4-position of the substituted pyridine ring 3 、-OCH 3 、-N(CH 3 ) 2 or -CF 3 , more specifically, one of the following groups represented by the substitution position on the pyridine ring: 4-Cl-, 4-F-, 4-CH 3 -、4-OCH 3 -、4-N(CH 3 ) 2 -、4-CF 3 -. R 2 , R 4 , R 6 Can be the same or different.

[0049] In some embodiments of the present invention, R 7 represents a substituent in Formula 1. Preferably, R 7 H, -CH 3 、-CH 2 CH 3 , -Cl or -C 6 H5 .

[0050] In some embodiments of the present invention, preferably, the aluminum-containing cocatalyst-1 is selected from at least one of methylaluminoxane (MAO), triisobutylaluminum-modified methylaluminoxane (MMAO), diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride, preferably selected from at least one of methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, diisobutylaluminum chloride, ethylaluminum dichloride, and sesquiethylaluminum. The polymerization reaction of ethylene monomer is initiated.

[0051] In some embodiments of the present invention, preferably, the aluminum-containing co-catalyst-2 is selected from at least one of diethylaluminum chloride, ethylaluminum sesquichloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride, preferably diisobutylaluminum chloride, ethylaluminum dichloride, and ethylaluminum sesquichloride. The copolymerization reaction of 1,3-butadiene monomer and polyethylene is initiated.

[0052] In some embodiments of the present invention, preferably, the molar ratio of the catalyst: aluminum-containing cocatalyst-1: aluminum-containing cocatalyst-2 is 1: (15-1000): (20-1000), preferably 1: 20-900: 40-900. The reactivity of the polymerization reaction and copolymerization reaction in steps (1) and (3) can be controlled, and the content of the ethylene structure segment, the butadiene structure segment, and the content of the cis-1,4-structure in the obtained copolymer can be controlled.

[0053] In some embodiments of the present invention, preferably, the organic solvent is selected from at least one of n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decahydronaphthalene, dodecane and hydrogenated gasoline, preferably toluene.

[0054] In some embodiments of the present invention, preferably, in step (1), the polymerization temperature is 20-70°C, preferably 30-60°C; the polymerization pressure is 1-70 bar, preferably 2.5-50 bar; the polymerization time is 1-80 min, preferably 2-60 min. The pressure may be the gas phase pressure of the ethylene monomer fed.

[0055] In some embodiments of the present invention, preferably, in step (3), in the polymerization system obtained in step (2), the concentration of 1,3-butadiene is 0.4-12 mol / L, preferably 0.6-9 mol / L; the copolymerization temperature is 30-70°C, preferably 40-60°C; the copolymerization pressure is 1-10 bar, preferably 2-5 bar; the copolymerization time is 0.5-5 h, preferably 1-4 h. The pressure can be the gas phase pressure of the 1,3-butadiene monomer fed. The concentration of 1,3-butadiene is limited to limit the amount of solvent used.

[0056] In some embodiments of the present invention, the amount relationship between ethylene monomer and butadiene can be controlled by the time and pressure of the ethylene monomer being introduced into the reaction, thereby obtaining a composite material with cis-1,4-butadiene rubber as an elastomer substrate and polyethylene as a reinforcing phase. Preferably, the weight relationship of the ethylene monomer and the butadiene monomer meets the amount of the corresponding polyethylene segment and the cis-1,4-butadiene rubber segment in the obtained copolymer, for example, based on the total weight of the copolymer, the weight ratio of the polyethylene segment and the cis-1,4-butadiene rubber segment is 0.1:99.9-80:20, preferably 1:99-75:25; in the cis-1,4-butadiene rubber segment, based on the total amount of the cis-1,4-butadiene rubber segment, the content is 90-98.5 mol%, preferably 92-98 mol%.

[0057] In the present invention, when the copolymerization reaction needs to be terminated, the following steps may also be performed:

[0058] When the copolymerization reaction reaches a suitable time, a stabilizer and a terminator are added in sequence to terminate the copolymerization reaction, and then the obtained product is washed, dissolved, and vacuum dried to obtain the ethylene-reinforced butadiene rubber.

[0059] The stabilizer may be a reagent that has an antioxidant effect, and may be a toluene solution of 2,2-methylenebis-(4-methyl-6-tert-butylphenol) with a mass concentration of 5%, and may be added in an amount of 0.5%-1.0% of the total weight of the monomer. The terminator may be a reagent that terminates polymerization and removes residual catalysts, and may be a methanol solution of hydrochloric acid with a mass concentration of 4%, and may be added in an amount of 0.1%-1.0% of the total weight of the monomer. The washing process may be using a methanol solution and water in sequence for about 3 times.

[0060] The preparation method provided by the present invention may specifically include:

[0061] The reaction equipment is operated with double-row pipes to purify the polymerization reaction environment; the cobalt-based catalyst and the organic solvent provided by the present invention are added to the reaction equipment, stirred and dispersed evenly, and heated to a set temperature; then ethylene monomer is introduced into the reaction equipment at a pressure of 1-70 bar, and after maintaining a constant pressure, a set amount of aluminum-containing cocatalyst-1 is added to initiate ethylene polymerization reaction, and the polymerization reaction time is determined according to the different ethylene segment content in the copolymer finally obtained;

[0062] After reaching the set polymerization reaction time, stop introducing ethylene monomer and instead add purified 1,3-butadiene monomer, remove the residual ethylene monomer and increase the pressure to 1-10 bar; add aluminum-containing co-catalyst-2 to initiate copolymerization of 1,3-butadiene monomer and polyethylene active chain segments, and maintain constant pressure for the set time;

[0063] Finally, a stabilizer and a terminator are added to terminate the reaction; the obtained product is then washed and dissolved with a methanol solution and an organic solvent three times in sequence, and then vacuum dried to obtain the polyethylene in-situ reinforced butadiene rubber.

[0064] The third aspect of the present invention provides a copolymer prepared by the preparation method of the present invention.

[0065] In some embodiments of the present invention, preferably, the copolymer is as described above and will not be described in detail.

[0066] A fourth aspect of the present invention provides a vulcanized rubber prepared from the copolymer of the present invention.

[0067] A fifth aspect of the present invention provides a use of the vulcanized rubber of the present invention in a tire, a shoe sole, a conveyor belt, a hose, or a sealing gasket.

[0068] In order to clearly describe the reaction process of the present invention, the process of preparing the copolymer will be described in detail below in conjunction with examples, but the following examples do not limit the entire protection scope of the present invention.

[0069] 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 a sample of about 5-10 mg, a nitrogen atmosphere throughout the process, the polymer was first heated to 200-220°C at a rate of 10°C / min, kept at a constant temperature for 2 minutes to eliminate thermal history, then cooled to 50°C at a rate of 10°C / min, and finally heated again to 210°C at the same rate;

[0070] The GPC data were measured using a PL triple detector instrument, and the test conditions included: the sample was dissolved in trichlorobenzene (1 mg / mL) at 150 °C, with polystyrene as the standard;

[0071] The breaking strength of the vulcanized rubber was tested in accordance with the national standard "GB / T 528-2009", and the tensile testing machine model was AG-20KNG produced by Shimadzu Corporation; the tearing strength was tested in accordance with the national standard "GB / T 529-2008", and the tensile testing machine model was AG-20KNG produced by Shimadzu Corporation;

[0072] The infrared spectrum test was conducted using the ATR-FTIR method using a Nicolet 6700 infrared spectrometer;

[0073] The NMR spectra were recorded at room temperature using a Unity-400 NMR instrument from Varian, USA, with deuterated chloroform or deuterated tetrachloroethane as the solvent. 1 H NMR (400MHz), 13 C NMR (100 MHz), TMS was used as the internal standard.

[0074] Example 1

[0075] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH(CH 3 ) 2 -(other substitution positions on the benzene ring are H), R 2 is H (all substitution positions on the pyridine ring are H), R 7 is methyl, X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 30°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then methylaluminoxane (MAO) (0.679mol) is added to initiate ethylene polymerization, and the introduction of ethylene monomer is stopped after 5min of polymerization;

[0076] 1,3-Butadiene monomer was introduced into the polymerization equipment to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 300g of 1,3-butadiene was added, and a constant pressure (3 bar) atmosphere was maintained. Diisobutylaluminum chloride (0.679mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization temperature was 45°C and the copolymerization time was 2h. Then, a toluene solution of 2,2-methylenebis-(4-methyl-6-tert-butylphenol) with a mass concentration of 5% was added as a stabilizer. Then, 20mL of a methanol solution of hydrochloric acid with a mass concentration of 4% was added to the polymerization system to terminate the reaction. Finally, the polymerization product was washed with methanol for 3 times and vacuum dried to obtain 255.9g of a copolymer.

[0077] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(The spectrum is as follows Figure 2The characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1650 and 736 and the polyethylene segment with wave number of 720 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak was 5.4 and the chemical shift of ethylene segment peak was 1.10 in the spectrum); the polyethylene segment content was 3.5wt%, and the cis-1,4-butadiene rubber segment content was 96.5wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 97.7mol%;

[0078] DSC test data, such as Figure 1 As shown, the copolymer has Tg=-109.9°C, Tm=133.4°C, Tc=118.3°C, and a crystallinity of 2.5%. According to GPC test data, the number average molecular weight of the copolymer is 174,000 g / mol, and the distribution is 2.93. The breaking strength of the vulcanized rubber is 15.7 MPa.

[0079] Example 2

[0080] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH(CH 3 ) 2 -(other substitution positions on the benzene ring are H), R 2 4-OCH 3 -(while the other substitution positions on the pyridine ring are H), R 7 is methyl, X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 39°C, ethylene monomer is introduced to maintain a constant pressure (4.9bar) ​​atmosphere, and then methylaluminoxane (MAO) (1.36mol) is added to initiate ethylene polymerization, and the introduction of ethylene monomer is stopped after 2 minutes of polymerization;

[0081] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 500 g of 1,3-butadiene was added, and a constant pressure (2 bar) atmosphere was maintained. 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.

[0082] The polymerization product was post-treated according to the method of Example 1 to obtain 485.9 g of copolymer.

[0083] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1)(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1644 and 734 and the polyethylene segment with wave number of 719 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 were obtained in the spectrum); the polyethylene segment content was 1.3wt%, and the cis-1,4-butadiene rubber segment content was 98.7wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 98.0mol%;

[0084] From the DSC test data, it can be seen that the Tg of the copolymer is -111.7°C, Tm is 127.3°C, Tc is 109.6°C, and the crystallinity is 0.9%; from the GPC test data, the number average molecular weight of the copolymer is 336,000 g / mol, and the distribution is 2.75; the breaking strength of the vulcanized rubber is 13.1 MPa.

[0085] Example 3

[0086] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 3 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,4,6-CH 3 -(other substitution positions on the benzene ring are H), R 2 is 4-F- (while the other substitution positions on the pyridine ring are H), R 7 is methyl, X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 35°C, and ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then diethylaluminum chloride (0.113mol) is added to initiate ethylene polymerization, and the polymerization reaction time is 10min, and then the introduction of ethylene monomer is stopped;

[0087] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 650 g of 1,3-butadiene was added, and a constant pressure (4 bar) atmosphere was maintained. Diisobutylaluminum chloride (0.679 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 50°C and the copolymerization reaction time was 2 h.

[0088] The polymerization product was post-treated according to the method of Example 1 to obtain 595.1 g of copolymer.

[0089] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1)(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1644 and 738 and the polyethylene segment with wave number of 720 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 1.7wt%, and the cis-1,4-butadiene rubber segment content was 98.3wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 97.8mol%;

[0090] From the DSC test data, it can be seen that the Tg of the copolymer is -107.9°C, Tm is 129.4°C, Tc is 111.5°C, and the crystallinity is 1.2%. From the GPC test data, the number average molecular weight of the copolymer is 411,000 g / mol, and the distribution is 2.82; the breaking strength of the vulcanized rubber is 14.1 MPa.

[0091] Example 4

[0092] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 4 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 is 2,6-F- (other substitution positions on the benzene ring are H), R 2 4-CF 3 -(while the other substitution positions on the pyridine ring are H), R 7 is ethyl, X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 30°C, ethylene monomer is introduced to maintain a constant pressure (24bar) atmosphere, and then methylaluminoxane (MMAO) (0.679mol) is added to initiate ethylene polymerization, and the introduction of ethylene monomer is stopped after 7min of polymerization;

[0093] 1,3-butadiene monomer was introduced into the polymerization equipment to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 930 g of 1,3-butadiene was added, and a constant pressure (2.5 bar) atmosphere was maintained. Diisobutylaluminum chloride (0.679 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 50°C and the copolymerization reaction time was 4 h.

[0094] The polymerization product was post-treated according to the method of Example 1 to obtain 995.1 g of copolymer.

[0095] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1)(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1647 and 741 and the polyethylene segment with wave number of 722 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 8.2wt%, and the cis-1,4-butadiene rubber segment content was 91.8wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 96.5mol%;

[0096] From the DSC test data, it can be seen that the Tg of the copolymer is -113.9°C, Tm is 132.8°C, Tc is 114.1°C, and the crystallinity is 6.1%. From the GPC test data, the number average molecular weight of the copolymer is 677,000 g / mol, and the distribution is 3.11; the breaking strength of the vulcanized rubber is 16.1 MPa.

[0097] Example 5

[0098] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH 2 CH 3 -(other substitution positions on the benzene ring are H), R 2 4-CH 3 -(while the other substitution positions on the pyridine ring are H), R 7 is H, X is bromine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 40°C, ethylene monomer is introduced to maintain a constant pressure (5.9bar) ​​atmosphere, and then methylaluminoxane (MAO) (1.131mol) is added to initiate ethylene polymerization, and the reaction time is 9min and then the introduction of ethylene monomer is stopped;

[0099] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 200 g of 1,3-butadiene was added, and a constant pressure (5 bar) atmosphere was maintained. 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 h.

[0100] The polymerization product was post-treated according to the method of Example 1 to obtain 201.7 g of copolymer.

[0101] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1)(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1649 and 741 and the polyethylene segment with wave number of 721 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 were obtained in the spectrum); the polyethylene segment content was 5.7wt%, and the cis-1,4-butadiene rubber segment content was 94.3wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 97.2mol%;

[0102] From the DSC test data, it can be seen that the Tg of the copolymer is -106.9°C, Tm is 134.2°C, Tc is 115.9°C, and the crystallinity is 4.2%. From the GPC test data, the number average molecular weight of the copolymer is 142,000 g / mol, and the distribution is 3.04; the breaking strength of the vulcanized rubber is 14.7MPa.

[0103] Example 6

[0104] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH 2 CH 3 -(other substitution positions on the benzene ring are H), R 2 4-N(CH 3 ) 2 -(while the other substitution positions on the pyridine ring are H), R 7 is phenyl, X is chlorine) (2.260mmol), using mechanical stirring to quickly stir the mixed system to disperse uniformly; heating the uniformly dispersed mixed system to 33°C, introducing ethylene monomer to maintain a constant pressure (5bar) atmosphere, and then adding modified methylaluminoxane (MMAO) (1.584mol) to initiate ethylene polymerization, and the reaction time is 18min; stopping the introduction of ethylene monomer;

[0105] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 280 g of 1,3-butadiene was added, and a constant pressure (3 bar) atmosphere was maintained. Diisobutylaluminum chloride (1.584 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 53°C and the copolymerization reaction time was 2 h.

[0106] The polymerization product was post-treated according to the method of Example 1 to obtain 301.7 g of copolymer.

[0107] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1648 and 737 and the polyethylene segment with wave number of 723 appeared in the spectrum); H-NMR spectrum (ppm) (the spectrum was as follows Figure 5The peak of cis-1,4-butadiene rubber with a chemical shift of 5.4 and the peak of ethylene segment with a chemical shift of 1.10 are shown in the figure; the content of polyethylene segment is 12.9wt%, and the content of cis-1,4-butadiene rubber segment is 87.1wt%; the content of cis-1,4-structure in the cis-1,4-butadiene rubber segment is 96.0mol%;

[0108] From the DSC test data, it can be seen that the Tg of the copolymer is -110.1°C, Tm is 136.7°C, Tc is 115.2°C, and the crystallinity is 9.7%. From the GPC test data, the number average molecular weight of the copolymer is 208,000 g / mol, and the distribution is 3.40; the breaking strength of the vulcanized rubber is 15.0 MPa.

[0109] Example 7

[0110] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2-C(CH 3 ) 3 -6-CH 3 -(other substitution positions on the benzene ring are H), R 2 is 4-Cl- (while the other substitution positions on the pyridine ring are H), R 7 is chlorine, X is bromine) (2.260mmol), use mechanical stirring to quickly stir the mixed system to disperse uniformly; heat the uniformly dispersed mixed system to 37°C, introduce ethylene monomer to maintain a constant pressure (4bar) atmosphere, then add diethylaluminum chloride (45.2mmol) to initiate ethylene polymerization, the reaction time is 60min; then stop introducing ethylene monomer;

[0111] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 450 g of 1,3-butadiene was added, and a constant pressure (2.2 bar) atmosphere was maintained. Diisobutylaluminum chloride (2.036 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 54°C and the copolymerization reaction time was 3 h.

[0112] The polymerization product was post-treated according to the method of Example 1 to obtain 502.3 g of copolymer.

[0113] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1639 and 740 and the polyethylene segment with wave number of 722 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 were obtained in the spectrum); the polyethylene segment content was 4.9wt%, and the cis-1,4-butadiene rubber segment content was 95.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 95.8mol%;

[0114] From the DSC test data, it can be seen that the Tg of the copolymer is -108.5°C, Tm is 133.2°C, Tc is 112.5°C, and the crystallinity is 3.6%. From the GPC test data, the number average molecular weight of the copolymer is 350,000 g / mol, and the distribution is 2.97; the breaking strength of the vulcanized rubber is 14.5 MPa.

[0115] Example 8

[0116] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 2 (wherein R 3 4,6-CH 3 -(R 3 The other substitution positions on the substituted pyridine ring are H), R 4 H(R 4 The substituted positions on the substituted pyridine ring are all H), X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 60°C, ethylene monomer is introduced to maintain a constant pressure (50bar) atmosphere, and then di-tert-butylaluminum chloride (0.113mol) is added to initiate ethylene polymerization, and the reaction time is 19min and then the introduction of ethylene monomer is stopped;

[0117] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 300 g of 1,3-butadiene was added. The atmosphere was kept at a constant pressure (3.5 bar). Diisobutylaluminum chloride (1.584 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 58° C. and the copolymerization reaction time was 3.5 h.

[0118] The polymerization product was post-treated according to the method of Example 1 to obtain 491.1 g of copolymer.

[0119] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1639 and 739 and the polyethylene segment with wave number of 720 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and 1.10 for ethylene segment appeared in the spectrum); the polyethylene segment content was 57.9wt%, and the cis-1,4-butadiene rubber segment content was 42.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 93.2mol%;

[0120] From the DSC test data, it can be seen that the Tg of the copolymer is -110.9°C, Tm is 139.2°C, Tc is 118.8°C, and the crystallinity is 46.3%; from the GPC test data, the number average molecular weight of the copolymer is 333,000, and the distribution is 5.10; the breaking strength of the vulcanized rubber is 17.7MPa.

[0121] Example 9

[0122] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 2 (wherein R 3 4-N(CH 3 ) 2 -6-CH 2 CH 3 -(R 3 The other substitution positions on the substituted pyridine ring are H), R 4 4-OCH 3 -(At the same time R 4 The other substitution position on the substituted pyridine ring is H), X is bromine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 50°C, and ethylene monomer is introduced to maintain a constant pressure (8bar) atmosphere, and then diethylaluminum chloride (0.684mol) is added to initiate ethylene polymerization, and the reaction time is 16min and then the introduction of ethylene monomer is stopped;

[0123] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 465 g of 1,3-butadiene was added. The atmosphere was kept at a constant pressure (3.5 bar). 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.

[0124] The polymerization product was post-treated according to the method of Example 1 to obtain 468.3 g of copolymer.

[0125] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1649 and 729 and the polyethylene segment with wave number of 719 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 were obtained in the spectrum); the polyethylene segment content was 26.5wt%, and the cis-1,4-butadiene rubber segment content was 73.5wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 94.7mol%;

[0126] From the DSC test data, it can be seen that the Tg of the in-situ reinforced butadiene rubber is -106.4°C, Tm is 137.7°C, Tc is 117.2°C, and the crystallinity is 20.2%. From the GPC test data, the number average molecular weight of the copolymer is 314,000 g / mol, and the distribution is 4.03. The breaking strength of the vulcanized rubber is 17.1 MPa.

[0127] Example 10

[0128] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 2 (wherein R 3 4-CF 3 -6-C 6 H 5 -(R 3 The other substitution positions on the substituted pyridine ring are H), R 4 4-F-(while R 4 The other substitution position on the substituted pyridine ring is H), X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 55°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then methylaluminoxane (MAO) (1.584mol) is added to initiate ethylene polymerization, and the introduction of ethylene monomer is stopped after 7 minutes of polymerization;

[0129] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 180 g of 1,3-butadiene was added, and a constant pressure (2.5 bar) atmosphere was maintained. Diisoethylaluminum chloride (1.584 mol) was injected to initiate a continuous copolymerization reaction of butadiene. The copolymerization reaction temperature was 55°C and the copolymerization reaction time was 1 hour.

[0130] The polymerization product was post-treated according to the method of Example 1 to obtain 191.1 g of copolymer.

[0131] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1646 and 741 and the polyethylene segment with wave number of 722 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 41.9wt%, and the cis-1,4-butadiene rubber segment content was 58.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 93.8mol%;

[0132] From the DSC test data, it can be seen that the Tg of the copolymer is -102.5°C, Tm is 138.6°C, Tc is 116.9°C, and the crystallinity is 32.7%; from the GPC test data, the number average molecular weight of the copolymer is 139,000 g / mol, and the distribution is 4.62; the breaking strength of the vulcanized rubber is 14.1 MPa.

[0133] Embodiment 11

[0134] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 1 L of toluene and a catalyst as shown in Formula 2 (wherein R 3 6-CH(C 6H 5 ) 2 -(R 3 The other substitution positions on the substituted pyridine ring are H), R 4 is 4-Cl (while R 4 The other substitution position on the substituted pyridine ring is H), X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 47°C, and ethylene monomer is introduced to maintain a constant pressure (2.9bar) ​​atmosphere, and then methylaluminoxane (MAO) (1.584mol) is added to initiate ethylene polymerization, and the reaction time is 14min; the introduction of ethylene monomer is stopped;

[0135] 1,3-Butadiene monomer was introduced into the polymerization equipment to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 150g of 1,3-butadiene was added, and a constant pressure (3 bar) atmosphere was maintained. Diethylaluminum chloride (1.584mol) was injected to initiate the copolymerization of the butadiene monomer. The copolymerization temperature was 50°C and the copolymerization time was 1h. A toluene solution of 2,2-methylenebis-(4-methyl-6-tert-butylphenol) with a mass concentration of 5% was added as a stabilizer. Then, 20mL of a methanol solution of hydrochloric acid with a mass concentration of 4% was added to the polymerization system to terminate the reaction. Finally, the polymerization product was washed and dissolved with a methanol solution and a toluene solvent in sequence for 3 times, and then vacuum dried to obtain 261.3g of a copolymer.

[0136] (2) Characterization of the obtained polyethylene in-situ reinforced butadiene rubber: FT-IR (KBr, cm -1 )(The spectrum is as follows Figure 4 The characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1647 and 731 and the polyethylene segment with wave number of 720 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak was 5.4 and the chemical shift of ethylene segment peak was 1.10 in the spectrum); the polyethylene segment content was 68.7wt%, and the cis-1,4-butadiene rubber segment content was 31.3wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 92.5mol%;

[0137] DSC test data, such as Figure 3 As shown, the copolymer has Tg = -110.6°C, Tm = 134.4°C; Tc = 115.1°C, and a crystallinity of 56.0%. According to GPC test data, the number average molecular weight of the copolymer is 183,000 g / mol, with a distribution of 5.75; and the breaking strength of the vulcanized rubber is 16.9 MPa.

[0138] Example 12

[0139] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 3 (wherein R 54-CH 3 -(the other substitution positions on the dihydrooxazole ring are H), R 6 is H (other substitution positions on the pyridine ring are H), X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 32°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then ethylaluminum dichloride (0.452mol) is added to initiate ethylene polymerization, and the reaction time is 20min and then the introduction of ethylene monomer is stopped;

[0140] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 190 g of 1,3-butadiene was added, and a constant pressure (3.2 bar) atmosphere was maintained. Diethylaluminum chloride (0.678 mol) was injected to initiate a continuous polymerization reaction of the butadiene monomer. The copolymerization reaction temperature was 48°C and the copolymerization reaction time was 1 hour.

[0141] The polymerization product was post-treated according to the method of Example 11 to obtain 391.1 g of copolymer.

[0142] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1648 and 741 and the polyethylene segment with wave number of 721 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 were obtained in the spectrum); the polyethylene segment content was 64.1wt%, and the cis-1,4-butadiene rubber segment content was 35.9wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 92.7mol%;

[0143] From the DSC test data, it can be seen that the Tg of the copolymer is -102.4°C, Tm is 140.2°C, Tc is 117.8°C, and the crystallinity is 51.9%. From the GPC test data, the number average molecular weight of the copolymer is 258,000 g / mol, and the distribution is 5.68; the breaking strength of the vulcanized rubber is 18.1 MPa.

[0144] Example 13

[0145] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 3 L of toluene and a catalyst as shown in Formula 3 (wherein R 5 4-CH 2 CH 3 -(the other substitution positions on the dihydrooxazole ring are H), R 6 4-CH 3-(while the other substituent on the pyridine ring is H), X is chlorine) (2.260mmol), using a mechanical stirrer to quickly stir the mixed system to disperse it uniformly; heating the uniformly dispersed mixed system to 42°C, introducing ethylene monomer to maintain a constant pressure (9bar) ​​atmosphere, and then adding methylaluminoxane (MAO) (1.584mol) to initiate ethylene polymerization, and stopping the introduction of ethylene monomer after 20min of ethylene polymerization;

[0146] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 408 g of 1,3-butadiene was added, and a constant pressure (2.5 bar) atmosphere was maintained. Diisobutylaluminum chloride (1.584 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 45°C and the copolymerization reaction time was 1.6 h.

[0147] The polymerization product was post-treated according to the method of Example 11 to obtain 491.9 g of copolymer.

[0148] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1647 and 738 and the polyethylene segment with wave number of 721 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 37.9wt%, and the cis-1,4-butadiene rubber segment content was 62.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 94.0mol%;

[0149] From the DSC test data, it can be seen that the Tg of the copolymer is -109.9°C, Tm is 136.3°C, Tc is 115.9°C, and the crystallinity is 29.6%. From the GPC test data, the number average molecular weight of the copolymer is 320,000 g / mol, and the distribution is 4.45; the breaking strength of the vulcanized rubber is 16.7MPa.

[0150] Embodiment 14

[0151] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 4 L of toluene and the catalyst shown in Formula 3 (where R 5 4-CH(CH 3 ) 2 -(the other substitution positions on the dihydrooxazole ring are H), R 6 4-OCH 3-(while the other substituent on the pyridine ring is H), X is chlorine) (2.260mmol), the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 50°C, ethylene monomer is introduced to maintain a constant pressure (40bar) atmosphere, and then sesquiethylaluminum (0.904mol) is added to initiate ethylene polymerization, and the reaction time is 18min and then the introduction of ethylene monomer is stopped;

[0152] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 150 g of 1,3-butadiene was added, and a constant pressure (4.2 bar) atmosphere was maintained. Ethyl aluminum sesquihydrate (0.904 mmol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 45°C and the copolymerization reaction time was 1 h.

[0153] The polymerization product was post-treated according to the method of Example 11 to obtain 431.5 g of copolymer.

[0154] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1649 and 733 and the polyethylene segment with wave number of 722 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 72.9wt%, and the cis-1,4-butadiene rubber segment content was 27.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 92.0mol%;

[0155] From the DSC test data, it can be seen that the Tg of the copolymer is -101.7°C, Tm is 142.1°C, Tc is 120.9°C, and the crystallinity is 60.0%; from the GPC test data, the number average molecular weight of the copolymer is 303,000 g / mol, and the distribution is 5.98; the breaking strength of the vulcanized rubber is 18.7 MPa.

[0156] Embodiment 15

[0157] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 3 (wherein R 5 For 4-C 6 H 5 -(the other substitution positions on the dihydrooxazole ring are H), R 6 4-CF 3-(the other substituent on the pyridine ring is H), X is chlorine) (2.260mmol), the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 45°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then methylaluminoxane (MAO) (1.131mol) is added to initiate ethylene polymerization, and the reaction time is 7min; the introduction of ethylene monomer is stopped;

[0158] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 908 g of 1,3-butadiene was added, and a constant pressure (4.5 bar) atmosphere was maintained. Ethyl aluminum sesquihydrate (1.131 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 40°C and the copolymerization reaction time was 4 hours.

[0159] The polymerization product was post-treated according to the method of Example 11 to obtain 847.9 g of copolymer.

[0160] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1646 and 738 and the polyethylene segment with wave number of 721 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 were obtained in the spectrum); the polyethylene segment content was 4.2wt%, and the cis-1,4-butadiene rubber segment content was 95.8wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 97.5mol%;

[0161] From the DSC test data, it can be seen that the Tg of the copolymer is -111.7°C, Tm is 128.1°C, Tc is 108.9°C, and the crystallinity is 3.0%. From the GPC test data, the number average molecular weight of the copolymer is 586,000 g / mol, and the distribution is 2.97; the breaking strength of the vulcanized rubber is 14.7 MPa.

[0162] Example 16

[0163] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH 3 -(other substituents on the benzene ring are H), R 2 is H (all substituents on the pyridine ring are H), R 7 is methyl, X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 38°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then methylaluminoxane (MAO) (1.584mol) is added to initiate ethylene polymerization, and the reaction time is 20min and then the introduction of ethylene monomer is stopped;

[0164] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 487 g of 1,3-butadiene was added, and a constant pressure (2.8 bar) atmosphere was maintained. Diisobutylaluminum chloride (1.584 mol) was injected to initiate the butadiene copolymerization reaction. The copolymerization reaction temperature was 45°C and the copolymerization reaction time was 3 h.

[0165] The polymerization product was post-treated according to the method of Example 11 to obtain 496.4 g of copolymer.

[0166] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1647 and 738 and the polyethylene segment with wave number of 721 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 21.1wt%, and the cis-1,4-butadiene rubber segment content was 79.9wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 95.0mol%;

[0167] From the DSC test data, it can be seen that the Tg of the in-situ reinforced butadiene rubber is -108.9°C, Tm is 135.2°C, Tc is 113.9°C, and the crystallinity is 16.0%. From the GPC test data, the number average molecular weight of the copolymer is 338,000 g / mol, and the distribution is 3.83; the breaking strength of the vulcanized rubber is 16.2MPa.

[0168] Embodiment 17

[0169] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH 2 CH 3 -(other substituents on the benzene ring are H), R 2 is H (all substituents on the pyridine ring are H), R 7 is methyl, X is bromine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 45°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then methylaluminoxane (MAO) (2.034mol) is added to initiate ethylene polymerization, and the reaction time is 20min and then the introduction of ethylene monomer is stopped;

[0170] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 463 g of 1,3-butadiene was added. The atmosphere was kept at a constant pressure (4 bar). 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 h.

[0171] The polymerization product was post-treated according to the method of Example 11 to obtain 377.9 g of copolymer.

[0172] (2) Characterization of the obtained polyethylene in-situ reinforced butadiene rubber: FT-IR (KBr, cm -1 )(the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1647 and 741 and the polyethylene segment with wave number of 722 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and the ethylene segment peak with a chemical shift of 1.10 appeared in the spectrum); the polyethylene segment content was 18.5wt%, and the cis-1,4-butadiene rubber segment content was 81.5wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 95.3mol%;

[0173] From the DSC test data, it can be seen that the Tg of the copolymer is -107.9°C, Tm is 134.5°C, Tc is 112.5°C, and the crystallinity is 14.0%; from the GPC test data, the number average molecular weight of the copolymer is 256,000 g / mol, and the distribution is 3.76; the breaking strength of the vulcanized rubber is 14.1 MPa.

[0174] Embodiment 18

[0175] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-CH(CH 3 ) 2 -(other substituents on the benzene ring are H), R 2 is 4-Cl (and the other substituents on the pyridine ring are H), R 7 is methyl, X is bromine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 36°C, ethylene monomer is introduced to maintain a constant pressure (4bar) atmosphere, and then diethylaluminum chloride (226mmol) is added to initiate ethylene polymerization, and the reaction time is 20min and then the introduction of ethylene monomer is stopped;

[0176] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 507 g of 1,3-butadiene was added, and a constant pressure (3.3 bar) atmosphere was maintained. 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 h.

[0177] The polymerization product was post-treated according to the method of Example 11 to obtain 467.1 g of copolymer.

[0178] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ), (the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1637 and 731 appeared in the spectrum, and the polyethylene segment with a wave number of 720 appeared); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and 1.10 for ethylene segment appeared in the spectrum); the polyethylene segment content was 7.9wt%, and the cis-1,4-butadiene rubber segment content was 92.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 96.6mol%;

[0179] From the DSC test data, it can be seen that the Tg of the copolymer is -105.9°C, Tm is 135.1°C, Tc is 115.9°C, and the crystallinity is 5.8%; from the GPC test data, the number average molecular weight of the copolymer is 317,000 g / mol, and the distribution is 3.08; the breaking strength of the vulcanized rubber is 13.9 MPa.

[0180] Embodiment 19

[0181] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,4,6-CH 3 -(other substituents on the benzene ring are H), R 2 is H (all substitution positions on the pyridine ring are H), R 7 The mixed system was uniformly dispersed by rapid stirring using a mechanical stirrer; the uniformly dispersed mixed system was heated to 43° C., ethylene monomer was introduced to maintain a constant pressure (5.9 bar) atmosphere, and then methylaluminoxane (MAO) (0.678 mol) was added to initiate ethylene polymerization, and the reaction time was 20 min, and then the introduction of ethylene monomer was stopped;

[0182] 1,3-butadiene monomer was introduced into the polymerization device to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 578 g of 1,3-butadiene was added, and a constant pressure (3.8 bar) atmosphere was maintained. 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 h.

[0183] The polymerization product was post-treated according to the method of Example 1 to obtain 531.7 g of copolymer.

[0184] (2) Characterization of the obtained copolymer: FT-IR (KBr, cm -1 ), (the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1647 and 741 and the polyethylene segment with wave number of 721 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and 1.10 for ethylene segment appeared in the spectrum); the polyethylene segment content was 9.9wt%, and the cis-1,4-butadiene rubber segment content was 10.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 96.2mol%;

[0185] From the DSC test data, it can be seen that the Tg of the copolymer is -110.8°C, Tm is 135.2°C, Tc is 117.9°C, and the crystallinity is 7.4%; from the GPC test data, the number average molecular weight of the copolymer is 373,000 g / mol, and the distribution is 3.28; the breaking strength of the vulcanized rubber is 15.3MPa.

[0186] Embodiment 20

[0187] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 2,6-C 6 H 5 -(other substituents on the benzene ring are H), R 2 is H (all substitution positions on the pyridine ring are H), R 7 is methyl, X is chlorine) (2.260mmol), and the mixed system is dispersed uniformly by rapid stirring with a mechanical stirrer; the uniformly dispersed mixed system is heated to 51°C, and ethylene monomer is introduced to maintain a constant pressure (2.7bar) atmosphere, and then modified methylaluminoxane (MMAO) (1.584mol) is added to initiate ethylene polymerization, and the introduction of ethylene monomer is stopped after 20min of ethylene polymerization;

[0188] 1,3-butadiene monomer was introduced into the polymerization equipment to purge the unpolymerized ethylene monomer. After the ethylene monomer was completely removed, 267 g of 1,3-butadiene was added, and a constant pressure (4 bar) atmosphere was maintained. Diisobutylaluminum chloride (1.584 mol) was injected to change the active center and initiate the polymerization reaction of the butadiene monomer. The copolymerization reaction temperature was 51°C and the copolymerization reaction time was 3 h.

[0189] The polymerization product was post-treated according to the method of Example 11 to obtain 247.1 g of copolymer.

[0190] (2) Characterization of the obtained polyethylene in-situ reinforced butadiene rubber: FT-IR (KBr, cm -1), (the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1644 and 739 and the polyethylene segment with wave number of 720 appeared in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a chemical shift of 5.4 and 1.10 for ethylene segment appeared in the spectrum); the polyethylene segment content was 24.9wt%, and the cis-1,4-butadiene rubber segment content was 75.1wt%; in the cis-1,4-butadiene rubber segment, the content of cis-1,4-structure was 94.7mol%;

[0191] From the DSC test data, it can be seen that the Tg of the copolymer is -105.3°C, Tm is 136.7°C, Tc is 114.8°C, and the crystallinity is 19.0%; from the GPC test data, the number average molecular weight of the copolymer is 166,000 g / mol, and the distribution is 3.91; the breaking strength of the vulcanized rubber is 16.0 MPa.

[0192] Comparative Example 1

[0193] (1) The polymerization reaction equipment was circulated three times using the double-row pipe operation technology, and then 2 L of toluene and a catalyst as shown in Formula 1 (wherein R 1 =2,4,6-CH 3 -(other substituents on the benzene ring are H), R 2 is H (all substitution positions on the pyridine ring are H), R 7 is methyl, X is bromine) (2.260mmol), use mechanical stirring to quickly stir the mixed system to disperse evenly; heat the evenly dispersed mixed system to 70°C, add 209g of 1,3-butadiene, maintain a constant pressure (3bar) atmosphere, inject diisobutylaluminum chloride (1.584mol) to initiate the polymerization of butadiene monomer, and the reaction time is 4h;

[0194] The polymerization product was post-treated according to the method of Example 11 to obtain 189.7 g of butadiene rubber.

[0195] (2) Characterization of the obtained butadiene rubber: FT-IR (KBr, cm -1 ), (the characteristic peaks of cis-1,4-butadiene rubber with wave numbers of 1644 and 739 were obtained in the spectrum); H-NMR spectrum (ppm) (the chemical shift of cis-1,4-butadiene rubber peak with a value of 5.4 was obtained in the spectrum); the content of cis-1,4-butadiene rubber segment was 100.0wt%; the content of cis-1,4-structure was 98.2mol%.

[0196] From the DSC test data, it can be seen that the Tg of the butadiene rubber is -109.5°C; from the GPC test data, the number average molecular weight of the copolymer is 129,000 g / mol, and the distribution is 2.68; the breaking strength of the vulcanized rubber is 8.5 MPa.

[0197] Comparative Example 2

[0198] The butadiene rubber prepared in Comparative Example 1 was blended with a polyethylene solution to prepare 124.6 g of a blend having a polyethylene content of 8.2% (compared with Example 4).

[0199] From the DSC test data, it can be seen that the Tg of the blend is -108.1°C, Tm is 138.7°C, Tc is 121.5°C, the crystallinity is 5.5%, and the breaking strength of the vulcanized rubber is 10.5 MPa.

[0200] Comparative Example 3

[0201] The butadiene rubber prepared in Comparative Example 1 was blended with a polyethylene solution to prepare 100.6 g of a blend having a polyethylene content of 12.9% (compared with Example 6).

[0202] From the DSC test data, it can be seen that the Tg of the blend is -107.5°C, Tm is 140.7°C, Tc is 121.7°C, the crystallinity is 9.0%, and the breaking strength of the vulcanized rubber is 11.1 MPa.

[0203] Comparative Example 4

[0204] The butadiene rubber prepared in Comparative Example 1 was blended with a polyethylene solution to prepare 85.6 g of a blend having a polyethylene content of 4.9% (compared with Example 7).

[0205] From the DSC test data, it can be seen that the Tg of the blend is -107.0°C, Tm is 139.2°C, Tc is 121.0°C, the crystallinity is 2.9%, and the breaking strength of the vulcanized rubber is 9.7 MPa.

[0206] The breaking strength of the vulcanized rubber obtained in Examples 1-20 and Comparative Examples 1-4 was measured by the following method:

[0207] Mixing and vulcanization: The copolymers prepared in Examples 1-20, and the butadiene rubber and the blends provided in the comparative examples were prepared into vulcanized rubber samples by the following methods:

[0208] Mixing process: All vulcanized rubber formulations were mixed in a Hapro RM-200A torque rheometer (Harbin Hapro Electrical Technology Co., Ltd.), and the mixed samples were passed through a two-roll mill for 20 times to obtain the final mixed rubber.

[0209] Preparation of vulcanized rubber samples: After the obtained mixed rubber was allowed to stand at room temperature for 24 hours, it was placed in a processing template and vulcanized in an XLB-D350×350 flat plate vulcanizer with the vulcanization temperature set at 150°C and t90 as the vulcanization time.

[0210] Table 1 Mixing conditions

[0211]

[0212] The prepared vulcanized rubber samples were measured according to the standard GB / T 528-1998 to obtain the breaking strength of the vulcanized rubber, and the tear strength of the vulcanized rubber was measured according to the standard GB / T529-1999 to obtain the tear strength of the vulcanized rubber. The results are shown in Table 2.

[0213] Table 2

[0214]

[0215]

[0216] Table 2 (continued)

[0217]

[0218] Table 2 (continued)

[0219]

[0220] Table 2 (continued)

[0221]

[0222]

[0223] Table 2 (continued)

[0224]

[0225] Note: 1 - glass transition temperature; 2 - melting temperature; 3 -Crystallization temperature

[0226] From the results in Table 2 and the comparison with the comparative examples, it can be seen that the copolymers prepared by the one-step polymerization method of Examples 1-20 have better reinforcement effects, and the fracture strength and tear strength of the vulcanized rubber are higher. Tm tends to increase with the increase of polyethylene content. Compared with Comparative Examples 2-4, polymers with the same ethylene content have lower Tm; crystallinity also tends to increase with the increase of polyethylene content, and with the increase of crystallinity, the fracture strength and tear strength of the vulcanized rubber tend to increase. Compared with Comparative Examples 2-4, polymers with the same ethylene content have higher crystallinity, and the fracture strength and tear strength are also higher. With the increase of polymer molecular weight, the strength of the vulcanized rubber also tends to increase. With the increase of ethylene content, the molecular weight distribution tends to increase.

[0227] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a copolymer, the method comprising: (1) In the presence of an organic solvent and a catalyst, an aluminum-containing cocatalyst-1 is used to initiate a polymerization reaction of ethylene monomer to obtain a polyethylene product; The aluminum-containing cocatalyst-1 is selected from at least one of methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride; (2) introducing 1,3-butadiene monomer into the polyethylene product and removing unreacted ethylene monomer; (3) adding an aluminum-containing co-catalyst-2 to the polymerization system obtained in step (2) to initiate a copolymerization reaction between 1,3-butadiene monomer and the polyethylene active chain segment in the polyethylene product to obtain the copolymer; the aluminum-containing co-catalyst-2 is selected from at least one of diethylaluminum chloride, sesquiethylaluminum, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride and n-octylaluminum dichloride; Wherein, in step (1), the catalyst is a compound having a structure shown in Formula 1, Formula 2 or Formula 3: Formula 1 Formula 2 Formula 3, Wherein, X is chlorine or bromine; R1 is H, or a substituent monosubstituted at position 2 or 4 on the benzene ring, or the same or different substituents disubstituted at positions 2, 4 or 2, 6 on the benzene ring, or the same or different substituents trisubstituted at positions 2, 4, and 6 on the benzene ring, wherein the substituent is -F, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C6H5 or -CH(C6H5)2; R3 is H, or -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C6H5 or -CH(C6H5)2 which are monosubstituted at the 6-position of the pyridine ring, or -CH3, -N(CH3)2 or -CF3 which are monosubstituted at the 4-position of the pyridine ring, or -CH3, -CH2CH3, -C6H5, -CH(C6H5)2, -N(CH3)2 or -CF3 which are disubstituted at the 4- and 6-positions of the pyridine ring, which are the same or different; R5 is H, or -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C6H5 or -CH(C6H5)2 which is monosubstituted at the 4-position of the dihydrooxazole ring; R2, R4, and R6 are each independently H, or -Cl, -F, -CH3, -OCH3, -N(CH3)2, or -CF3 which is monosubstituted at the 4-position of the pyridine ring; R7 is H, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -Cl, -C6H5 or -CH(C6H5)2; The molar ratio of the catalyst: the aluminum-containing co-catalyst-1: the aluminum-containing co-catalyst-2 is 1:15-1000:20-1000.

2. The preparation method according to claim 1, wherein The molar ratio of the catalyst: the aluminum-containing co-catalyst-1: the aluminum-containing co-catalyst-2 is 1:20-900:40-900.

3. The preparation method according to claim 1 or 2, wherein In step (1), the polymerization reaction temperature is 20-70° C.; the polymerization reaction pressure is 1-70 bar; and the polymerization reaction time is 1-80 min.

4. The preparation method according to claim 3, wherein In step (1), the polymerization reaction temperature is 30-60° C.; the polymerization reaction pressure is 2.5-50 bar; and the polymerization reaction time is 2-60 min.

5. The preparation method according to claim 1 or 2, wherein: The organic solvent is selected from at least one of n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decahydronaphthalene, dodecane and hydrogenated gasoline.

6. The preparation method according to claim 5, wherein: The organic solvent is toluene.

7. The preparation method according to claim 1 or 2, wherein: In step (3), the concentration of 1,3-butadiene in the polymerization system obtained in step (2) is 0.4-12 mol / L.

8. The preparation method according to claim 7, wherein: In step (3), the concentration of 1,3-butadiene in the polymerization system obtained in step (2) is 0.6-9 mol / L.

9. The preparation method according to claim 1 or 2, wherein: In step (3), the copolymerization reaction temperature is 30-70°C; the copolymerization reaction pressure is 1-10 bar; and the copolymerization reaction time is 0.5-5 h.

10. The preparation method according to claim 9, wherein: In step (3), the copolymerization reaction temperature is 40-60°C; the copolymerization reaction pressure is 2-5 bar; and the copolymerization reaction time is 1-4 h.

11. The preparation method according to claim 1 or 2, wherein: The aluminum-containing co-catalyst-1 is at least one selected from methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, diisobutylaluminum chloride, ethylaluminum dichloride, and ethylaluminum sesquichloride.

12. The preparation method according to claim 1 or 2, wherein: The aluminum-containing co-catalyst-2 is selected from at least one of diisobutylaluminum chloride, ethylaluminum dichloride, and ethylaluminum sesquichloride.

13. A copolymer obtained by the preparation method according to any one of claims 1 to 12.

14. A vulcanized rubber prepared from the copolymer according to claim 13.

15. Use of the vulcanized rubber according to claim 14 in tires, shoe soles, conveyor belts, hoses or sealing gaskets.

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