Butadiene-styrene-butadiene integrated rubber as well as preparation method and application thereof

Abstract

The invention discloses cis-butadiene-styrene integrated rubber as well as a preparation method and application thereof, and belongs to the field of synthetic rubber. The cis-butadiene-styrene integrated rubber is high cis-polybutadiene rubber polymerized styrene rubber synthesized by high cis-polybutadiene rubber and butadiene styrene through in-situ anionic polymerization; the high cis-polybutadiene rubber is synthesized by catalyzing butadiene to generate coordination polymerization by adopting a catalyst, the cis content is higher than 90%, and the polybutadiene rubber is prepared by initiating butadiene, styrene and polybutadiene rubber to generate anionic polymerization by adopting an anionic polymerization initiator; the mass ratio of the high cis-polybutadiene rubber to the polymerized styrene-butadiene rubber is 1: (0.05-95); the butadiene cis content in the polymerized styrene-butadiene rubber is 3-35%, the butadiene trans content in the polymerized styrene-butadiene rubber is 2-55%, the vinyl content in the polymerized styrene-butadiene rubber is 2-57%, the styrene content in the polymerized styrene-butadiene rubber is 1-30%, the weight-average molecular weight of the polymerized styrene-butadiene rubber is 0.5-1 million, the molecular weight distribution PDI is less than 2, and the conversion rate of the styrene is greater than 60%.

Description

Technical Field

[0001] The present invention relates to a synthetic rubber material, a method for preparing the synthetic rubber material, a process for preparing the synthetic rubber material, and applications of the synthetic rubber material, the method for preparing the synthetic rubber material, and the process for preparing the synthetic rubber material, and in particular relates to a cis-butylene-styrene integrated rubber, a method for preparing the cis-butylene-styrene integrated rubber, a process for preparing the cis-butylene-styrene integrated rubber, applications of the method for preparing the cis-butylene-styrene integrated rubber, applications of the process for preparing the cis-butylene-styrene integrated rubber, and applications of the cis-butylene-styrene integrated rubber; the cis-butylene-styrene integrated rubber is an integrated rubber or a special rubber. Background Art

[0002] Cis-1,4-butadiene rubber (CI-1,4-butadiene rubber) has excellent properties, including good elasticity, friction resistance, and low-temperature resistance, but poor wet-slip resistance. Styrene-butadiene rubber (SBR) has good wet-slip resistance, but relatively poor friction and low-temperature resistance, making it inferior to CI-1,4-butadiene rubber. The synthesis of CI-1,4-butadiene rubber involves the coordination polymerization of butadiene monomer using titanium, cobalt, nickel, or rare earth catalysts in the presence of cocatalysts such as alkylaluminum and BF3 etherate complexes, producing high-cis polybutadiene rubber. The active central atoms (Ti, Co, Ni, Nd, Pr, Ce, Y, etc.) of the titanium, cobalt, nickel, or rare earth catalysts simultaneously complex with the C1 and C4 atoms of the butadiene monomer to form large π bonds, resulting in a 1,4 polymerization reaction, producing high-cis polybutadiene rubber with a cis structure content exceeding 90%. While styrene can also undergo coordination polymerization to produce polystyrene under the action of a catalyst, the styrene molecule only has one double bond. The two carbon atoms, C1 and C2, on the double bond form a π bond with the active center atoms of a titanium, cobalt, nickel, or rare earth catalyst, leading to a 1,2 polymerization reaction to produce polystyrene. Because the coordination polymerization mechanism of butadiene differs from that of styrene, butadiene and styrene cannot be used to produce a butadiene-styrene copolymer through coordination polymerization. Even if butadiene and styrene are reacted in the same reactor, only a mixture of polybutadiene and polystyrene homopolymers is obtained.

[0003] The industry can produce various copolymers of butadiene and styrene through anionic polymerization using lithium-based initiators, including random and block copolymers. However, the butadiene monomer has a variety of structures within the polymer chain, with cis-containing monomers accounting for approximately 13-35%, trans-containing monomers for approximately 27-55%, vinyl monomers for approximately 12-57%, and styrene monomers for approximately 10-30%. Therefore, high-cis polybutadiene or high-cis butadiene-styrene copolymers cannot be produced through anionic polymerization.

[0004] The industry also has the use of high-cis polybutadiene and styrene-butadiene rubber blending, high-cis polybutadiene and styrene-butadiene rubber are mixed in an organic solvent according to a certain ratio to obtain a high-cis polybutadiene and styrene-butadiene rubber composite rubber. Although the advantages of the two rubbers can be blended together to a certain extent to obtain a composite rubber with improved wear resistance and wet-slip resistance, the two rubbers cannot be mixed at the molecular level by this simple mixing method, and phase separation easily occurs, resulting in unstable performance. Therefore, the preparation technology of the integrated rubber of cis-1,1-butadiene rubber and styrene-butadiene rubber is key. The inventor of the present invention, Huang Sihuang, has proposed a new production process, which adds a storage tank after the post-polymerization reactor of the high-cis polybutadiene rubber synthesis reactor, and then connects the anionic polymerization process of butadiene-styrene. Anionic copolymerization reaction occurs with the polybutadiene rubber molecules containing double bonds produced in the high-cis polybutadiene rubber synthesis reactor, achieving a cis-1,1-butadiene integrated rubber in which the polybutadiene rubber molecules and the styrene-butadiene rubber molecules are chemically bonded, producing an integrated rubber of high-cis polybutadiene rubber and styrene-butadiene rubber.

[0005] The present invention unexpectedly discovered that a storage tank is added after the post-polymerization reactor of the high-cis polybutadiene rubber synthesis reactor, the temperature is maintained constant and stirring is carried out to terminate the coordination polymerization reaction of butadiene, and then a butadiene-styrene solution anionic polymerization process is connected, styrene and anionic initiator are added, butadiene is replenished, and a polarity regulator is added to cause anionic copolymerization of butadiene, styrene, and polybutadiene rubber, and a butadiene-styrene-polybutadiene rubber copolymer is generated in situ in the high-cis polybutadiene rubber solution. A chain extender is added to the last polymerization reactor in the anionic polymerization process to prepare a cis-butylene-butadiene-styrene integrated rubber.

[0006] The accidental discovery of the present invention can also be used for the integrated synthesis of polymer materials of other two or more rubbers or other two or more resins or other two or more fibers; a storage tank is added after the EPDM post-polymerization kettle to maintain the temperature constant and stir, terminate the coordination polymerization reaction of EPDM, and then connect the butadiene styrene solution anionic polymerization process, or connect any other solution polymerization process to prepare EPDM rubber and styrene butadiene rubber integrated rubber; a storage tank is added after the POE polymerization kettle to maintain the operating temperature constant and stir the anionic polymerization process, terminate the coordination polymerization reaction of POE, and then connect the butadiene styrene solution anionic polymerization process, or connect any other solution polymerization process to prepare EPDM rubber and styrene butadiene rubber integrated rubber. A solution polymerization process is carried out to prepare POE elastomer styrene butadiene rubber integrated rubber; a storage tank is added after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis kettle to maintain the operating temperature of the free radical polymerization process unchanged and stir, and then connect the acrylonitrile styrene melt method or solution method free radical polymerization process to produce high-cis butadiene rubber and SAN resin integrated rubber and plastic materials; a storage tank is added after the POE polymerization kettle to maintain the operating temperature of the melt method free radical polymerization process unchanged and stir, terminate the coordination polymerization reaction of POE, and then connect the butadiene acrylonitrile melt method or solution method free radical polymerization process, or connect any other solution polymerization process to produce POE elastomer nitrile butadiene rubber integrated rubber, etc. The present invention can smoothly prepare other rubber and rubber integrated rubber materials, rubber and resin integrated rubber and plastic materials, rubber and fiber integrated rubber and fiber materials, resin and resin integrated resin materials, resin and fiber integrated plastic and fiber materials or fiber and fiber integrated fiber materials; the polymerization process is a coordination polymerization process, anionic polymerization process, cationic polymerization process, free radical polymerization process, condensation polymerization process, ring-opening polymerization process or other polymerization process; the other rubbers, resins or fibers include but are not limited to the following materials: polyethylene, polypropylene, polystyrene, polyvinyl chloride, poly 1-butene (PB), ethylene / 1-octene copolymer (POE), ABS, ASA, HIPS, styrene / maleic anhydride copolymer (SMA), EPR, EPDM, NBR, HNBR, SBS, SIS, SEBS, SEIS, SIBR, ESBR, SSBR, IIR, IR, NR, BR, CR, PBE, PC, PET, PBT, polybutylene succinate (PBS), polybutylene succinate / adipate (PBSA), polybutylene adipate / terephthalate (PBAT), PA, PEK, PPO, PTMEG, HTPB, PU, ​​PTFE, PMMA, PVA, ACM, PPS, EVA, ethylene / MMA copolymer (EMMA), ethylene / methacrylic acid copolymer (EMAA), PHB, PTT, PEN, PCT, PLA, PAN, PBI, PBO, POM or unterminated POM, etc. Summary of the Invention

[0007] One of the purposes of the present invention is to provide a cis-butadiene-styrene integrated rubber, wherein the cis-butadiene-styrene integrated rubber is a high-cis polybutadiene rubber and a polybutadiene-styrene integrated rubber synthesized by copolymerizing high-cis polybutadiene rubber and butadiene styrene;

[0008] One of the objectives of the present invention is to provide a method for preparing a cis-1,2-butadiene-styrene integrated rubber. The method comprises the following steps: adding a storage tank after a post-polymerization reactor of a high-cis polybutadiene rubber synthesis reactor, maintaining a constant temperature and stirring, terminating a coordination polymerization reaction of butadiene, then connecting a butadiene-styrene solution anionic polymerization process, adding styrene and an anionic initiator, replenishing butadiene, adding a polarity regulator, causing an anionic copolymerization reaction of butadiene-styrene-polybutadiene, in-situ generating a butadiene-styrene-polybutadiene copolymer in a high-cis polybutadiene rubber solution, and adding a chain extender to the last polymerization reactor of the anionic polymerization process to prepare the cis-1,2-butadiene-styrene integrated rubber.

[0009] One of the objectives of the present invention is to provide a cis-1,2-butadiene-styrene integrated rubber preparation process. The cis-1,2-butadiene-styrene integrated rubber preparation process comprises: adding a storage tank after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis process, and connecting the storage tank to the styrene-butadiene rubber anion polymerization process; wherein the high-cis polybutadiene rubber synthesis process is composed of 1-5 polymerization kettles; wherein the storage tank is used to add a terminator to terminate the coordination polymerization reaction of butadiene, and styrene, anionic initiator, butadiene supplement, polarity regulator, etc. are added to the same storage tank; wherein the styrene-butadiene rubber anion polymerization process is composed of 1-3 polymerization kettles, and a chain extender or other commonly used additives are added to the post-polymerization kettle of the anionic polymerization process.

[0010] One of the purposes of the present invention is to provide a method for preparing an integrated material of two or more other rubbers, two or more other resins, or two or more other fibers. A storage tank is added after the EPDM post-polymerization reactor to maintain the temperature constant and stir, terminate the coordination polymerization reaction of EPDM, and then connect the butadiene styrene solution anionic polymerization process, or connect any other solution polymerization process to prepare an EPDM and styrene butadiene rubber integrated rubber; a storage tank is added after the POE polymerization reactor to maintain the operating temperature of the anionic polymerization process constant and stir, terminate the coordination polymerization reaction of POE, and then connect the butadiene styrene solution anionic polymerization process, or connect other Any solution polymerization process can prepare POE elastomer styrene butadiene rubber integrated rubber; a storage tank is added after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis kettle to maintain the operating temperature of the free radical polymerization process unchanged and stir, and then connect the acrylonitrile styrene melt method or solution method free radical polymerization process to produce high-cis butadiene rubber and SAN resin integrated rubber and plastic materials; a storage tank is added after the POE polymerization kettle to maintain the operating temperature of the melt method free radical polymerization process unchanged and stir, terminate the coordination polymerization reaction of POE, and then connect the butadiene acrylonitrile melt method or solution method free radical polymerization process, or connect any other solution polymerization process to produce POE elastomer nitrile butadiene rubber integrated rubber, etc. The present invention can smoothly prepare other rubber and rubber integrated rubber materials, rubber and resin integrated rubber and plastic materials, rubber and fiber integrated rubber and fiber materials, resin and resin integrated resin materials, resin and fiber integrated plastic and fiber materials or fiber and fiber integrated fiber materials; the other rubbers, resins or fibers include but are not limited to the following materials: polyethylene, polypropylene, polystyrene, polyvinyl chloride, poly 1-butene (PB), ethylene / 1-octene copolymer (POE), ABS, ASA, HIPS, styrene / maleic anhydride copolymer (SMA), EPR, EPDM, NBR, HNBR, SBS, SIS, SEBS, SEIS, SIB R, ESBR, SSBR, IIR, IR, NR, BR, CR, PBE, PC, PET, PBT, polybutylene succinate (PBS), polybutylene succinate / adipate (PBSA), polybutylene adipate / terephthalate (PBAT), PA, PEK, PPO, PTMEG, HTPB, PU, ​​PTFE, PMMA, PVA, ACM, PPS, EVA, ethylene / MMA copolymer (EMMA), ethylene / methacrylic acid copolymer (EMAA), PHB, PTT, PEN, PCT, PLA, PAN, PBI, PBO or POM, etc.

[0011] The cis-butadiene-styrene integrated rubber is a high-cis polybutadiene rubber and polybutadiene-styrene rubber synthesized by in-situ anionic polymerization of high-cis polybutadiene rubber and butadiene styrene; wherein the high-cis polybutadiene rubber is synthesized by coordination polymerization of butadiene catalyzed by a catalyst, and the cis content is higher than 90%, and the catalyst is a titanium catalyst, a cobalt catalyst, a nickel catalyst or a rare earth catalyst; wherein the polybutadiene-styrene rubber is prepared by anionic polymerization of butadiene, styrene and polybutadiene rubber initiated by an anionic polymerization initiator to prepare polybutadiene-styrene rubber (SSBR); The anionic polymerization initiator is a monolithium initiator, a dilithium initiator, a sodium initiator, a potassium initiator, etc.; the mass ratio of the high cis polybutadiene rubber to the polystyrene butadiene rubber is 1:(0.05-95); the cis content of butadiene in the polystyrene butadiene rubber is about 3-35%, the trans content of butadiene is about 2-55%, the vinyl content is about 2-57%, and the styrene content is about 1-30%. The weight average molecular weight of the styrene butadiene rubber is 0.5-1 million, the molecular weight distribution PDI is less than 2, and the conversion rate of styrene is greater than 60%.

[0012] The method for preparing the cis-1,4-dopamine-butadiene integrated rubber comprises the following steps: adding a storage tank after the post-polymerization reactor of the synthesis reactor of the high-cis polybutadiene rubber synthesis process, maintaining a constant temperature and stirring, terminating the coordination polymerization reaction of butadiene, then connecting the butadiene styrene solution anion polymerization process, adding styrene and anionic initiator, replenishing butadiene, adding a polarity regulator, causing butadiene styrene to undergo anionic polymerization, in-situ generating a butadiene styrene-polybutadiene rubber copolymer in the high-cis polybutadiene rubber solution, and adding a chain extender to the last polymerization reactor of the anionic polymerization process to prepare the cis-1,4-dopamine-butadiene integrated rubber, wherein the chain extender is a commonly used chain extender for anionic polymerization and is selected from silicon tetrachloride, tin tetrachloride, disilane hexachloride, and the like.

[0013] The preparation principle of the cis-1,4-butadiene-styrene integrated rubber is as follows: in the high-cis polybutadiene rubber synthesis process, the high-cis polybutadiene rubber is synthesized by the coordination polymerization principle; in the butadiene styrene anionic polymerization process, an anionic copolymerization reaction occurs with the double-bonded polybutadiene rubber molecules produced in the high-cis polybutadiene rubber synthesis process, thereby realizing the cis-1,4-butadiene-styrene integrated rubber in which the polybutadiene rubber molecules and the styrene butadiene rubber molecules are connected by chemical bonds, thereby producing an integrated rubber of high-cis polybutadiene rubber and styrene butadiene rubber, which is the cis-1,4-butadiene-styrene integrated rubber described in the present invention.

[0014] The integrated butadiene-styrene rubber preparation process is as follows: one or more rubber storage tanks are added after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis process, and the storage tanks are connected to the butadiene-styrene rubber anion polymerization process; wherein the high-cis polybutadiene rubber synthesis process is composed of 1-5 polymerization kettles; wherein the storage tank is used to add a terminator to terminate the coordination polymerization reaction of butadiene, and styrene, anionic initiator, butadiene supplement, and polarity regulator are added to the same storage tank; wherein the butadiene-styrene rubber anion polymerization process is composed of 1-3 polymerization kettles, and a chain extender or other commonly used additives are added to the polymerization kettle after the butadiene-styrene rubber anion polymerization process; wherein the integrated butadiene-styrene rubber preparation process is a continuous process, a semi-continuous process, or a batch process.

[0015] The invention discloses a process for preparing cis-butadiene-styrene integrated rubber, wherein the high cis polybutadiene rubber synthesis process comprises 1-5 polymerization kettles, a polymerization reaction time of 0.5-8 hours, a polymerization reaction temperature of 30-200° C., a polymerization kettle pressure of 0.1-1 MPa, and an inert organic solvent of C5-C 20 The organic solvent is selected from benzene, toluene, hexane, heptane, cyclohexane or their mixed solvents, the cis content of butadiene in the high cis-butadiene rubber is higher than 90%, the Mooney viscosity is 30-55, and the weight average molecular weight is 0.5-600,000; wherein the anionic polymerization process of the styrene-butadiene rubber is composed of 1-3 polymerization kettles, the polymerization temperature is 30-180 ° C ...

[0016] The polymerization time is 0.5-8 hours, the polymerization pressure is 0.2-5.0 MPa, the cis-butadiene content of the styrene-butadiene rubber is about 3-35%, the trans-butadiene content is about 2-55%, the vinyl content is about 2-57%, the styrene content is about 1-30%, the weight-average molecular weight of the styrene-butadiene rubber is 0.5-1 million, the molecular weight distribution PDI is less than 2, and the styrene conversion rate is greater than 60%.

[0017] The operation process of the olefin polymer elastomer bulk melt polymerization synthesis process is as follows:

[0018] (1) Butadiene, toluene and catalyst are added to a butadiene polymerization kettle of a high-cis-butadiene rubber synthesis process from a monomer butadiene preparation tank, an inert organic solvent toluene preparation tank and a catalyst preparation tank, respectively, wherein the weight ratio of butadiene to catalyst is 20,000:(0.1-10), and the weight ratio of toluene to butadiene is 1:(0.3-1.5); the polymerization reaction time is 0.5-8 hours, the polymerization reaction temperature is 30-200°C, the pressure of the polymerization kettle is 0.1-5MPa, the conversion rate of butadiene is 30-90%, the cis content of polybutadiene is higher than 90%, the Mooney viscosity is 30-55, and the weight average molecular weight is 0.5-600,000; the catalyst is a titanium catalyst, a cobalt catalyst, a nickel catalyst or a rare earth catalyst.

[0019] (2) Send the butadiene-styrene butadiene rubber solution into the rubber solution storage tank, maintain the storage tank at 30-180℃, stir, and add C2-C 20 Organic compounds containing heteroatoms adjust the polarity of the solvent and terminate the active centers of butadiene coordination polymerization;

[0020] (3) The rubber solution is fed into the anionic polymerization process of styrene-butadiene rubber, styrene is added from the styrene preparation tank, initiator is added from the anionic polymerization initiator preparation tank, and butadiene is added from the butadiene preparation tank. The weight ratio of styrene to initiator is 50,000:(0.1-10), and the weight ratio of butadiene to initiator is 10,000:(0.1-10). The polymerization temperature is 30-180° C., the polymerization time is 0.5-8 hours, and the polymerization pressure is 0.2-5.0 MPa. The cis content of butadiene in the styrene-butadiene rubber is about 3-35%, the trans content of butadiene is about 2-55%, the vinyl content is about 2-57%, and the styrene content is about 1-30%. The weight average molecular weight of the styrene-butadiene rubber is 0.5-1,000,000, the molecular weight distribution (PDI) is less than 2, and the conversion rate of styrene is greater than 60%.

[0021] (4) The rubber solution is fed into the post-polymerization reactor of the anionic polymerization process of styrene-butadiene rubber, stirred, and a chain extender is added. The polymerization temperature is 30-180°C, the polymerization time is 0.5-8 hours, and the polymerization pressure is 0.2-5.0 MPa; the chain extender is silicon tetrachloride, tin tetrachloride or disilane hexachloride, etc.

[0022] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, the butadiene-styrene integrated rubber is obtained.

[0023] The catalyst is a titanium catalyst, a cobalt catalyst, a nickel catalyst or a rare earth catalyst, and the preparation and aging of the catalyst are carried out in accordance with existing advanced technologies. The titanium catalyst is titanium naphthenate, titanium tetrachloride, dimethylsilyl-2,6-difluoroanilinocyclopentadiene titanium dichloride or 2,6-difluoroanilinocarbon-dimethylindene titanium dichloride, etc. The cobalt catalyst is cobalt naphthenate, the nickel catalyst is nickel naphthenate, and the rare earth catalyst is neodymium naphthenate, 2,6-difluoroanilinocarbon-dimethylindene neodymium chloride, cerium naphthenate, scandium naphthenate, samarium naphthenate or yttrium naphthenate; the anionic polymerization initiator is a monolithium initiator, a dilithium initiator, a sodium initiator, a potassium initiator, etc., and the preparation of the anionic polymerization initiator is carried out in accordance with existing advanced technologies; the C2-C 20 The organic compound containing heteroatoms is THF, ether, butyl ether, triethylamine, aniline or a mixture thereof; wherein the inert organic solvent is C5-C 20 The organic matter is selected from toluene, hexane, heptane, cyclohexane or a mixed solvent thereof.

[0024] The method and process for preparing the integrated butadiene-styrene butadiene rubber can also be used for preparing an integrated material of two or more other rubbers or two or more other resins or two or more other fibers. A storage tank is added after the EPDM post-polymerization kettle to maintain the temperature constant, stir, terminate the coordination polymerization reaction of EPDM, and then connect the anionic polymerization process of butadiene styrene solution method, or connect any other solution polymerization process to prepare the EPDM rubber and styrene butadiene rubber integrated rubber; a storage tank is added after the POE polymerization kettle to maintain the operating temperature of the anionic polymerization process constant, stir, terminate the coordination polymerization reaction of POE, and then connect the anionic polymerization process of butadiene styrene solution method. Or connect any other solution polymerization process to prepare POE elastomer styrene butadiene rubber integrated rubber; add a storage tank after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis kettle, maintain the operating temperature of the free radical polymerization process unchanged, stir, and then connect the acrylonitrile styrene melt method or solution method free radical polymerization process to produce high-cis butadiene rubber and SAN resin integrated rubber and plastic materials; add a storage tank after the POE polymerization kettle, maintain the operating temperature of the melt method free radical polymerization process unchanged, stir, terminate the coordination polymerization reaction of POE, and then connect the butadiene acrylonitrile melt method or solution method free radical polymerization process, or connect any other solution polymerization process to produce POE elastomer nitrile butadiene rubber integrated rubber, etc. The present invention can smoothly prepare other rubber and rubber integrated rubber materials, rubber and resin integrated rubber and plastic materials, rubber and fiber integrated rubber and fiber materials, resin and resin integrated resin materials, resin and fiber integrated plastic and fiber materials or fiber and fiber integrated fiber materials; the other rubbers, resins or fibers include but are not limited to the following materials: polyethylene, polypropylene, polystyrene, polyvinyl chloride, poly 1-butene (PB), ethylene / 1-octene copolymer (POE), ABS, ASA, HIPS, styrene / maleic anhydride copolymer (SMA), EPR, EPDM, NBR, HNBR, SBS, SIS, SEBS, SEIS, SIB R, ESBR, SSBR, IIR, IR, NR, BR, CR, PBE, PC, PET, PBT, polybutylene succinate (PBS), polybutylene succinate / adipate (PBSA), polybutylene adipate / terephthalate (PBAT), PA, PEK, PPO, PTMEG, HTPB, PU, ​​PTFE, PMMA, PVA, ACM, PPS, EVA, ethylene / MMA copolymer (EMMA), ethylene / methacrylic acid copolymer (EMAA), PHB, PTT, PEN, PCT, PLA, PAN, PBI, PBO or POM, etc.

[0025] The preparation method of the butadiene-styrene integrated rubber can also be extended to the production of integrated rubber or special rubber, wherein the integrated rubber or special rubber is suitable for various existing processing technologies, and is also suitable for various new processing technologies to be developed in the future, specifically extrusion, blow molding, unidirectional (bidirectional) film drawing, wet (dry) film forming, foaming, rotational molding, casting and other processing technologies, as well as various uses suitable for the processed products. The various uses are mainly used for automobile tires, battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant materials, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, vehicle interior decoration parts, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0026] The invention adds one or more storage tanks after the post-polymerization reactor of the high-cis polybutadiene rubber synthesis process, and then connects the butadiene styrene solution anionic polymerization process. This cleverly combines the high-cis polybutadiene rubber synthesis process and the butadiene styrene solution anionic polymerization process into a new polymerization process, thereby preparing new polymer materials such as cis-butadiene-butadiene styrene integrated rubber. This new polymer material is achieved through two or more different polymerization principles, breaking through the current polymer synthesis process based on a single polymerization principle. The difficulty of this patent is that the gel content of the high-cis polybutadiene rubber synthesized in the high-cis polybutadiene rubber synthesis process is required to be less than 1%, the gel content of the high-cis polybutadiene rubber during tank handling and storage is also required to be less than 2%, and the gel content of the first polymerization reactor in the butadiene styrene solution anionic polymerization process is required to be less than 2%.

[0027] The sequence distribution and microstructure of the copolymers were characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy, and the molecular weight and molecular weight distribution of the copolymers were characterized by gel permeation chromatography.

[0028] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the following embodiments. DETAILED DESCRIPTION

[0029] Example 1

[0030] (1) Add 0.1 g of titanium naphthenate catalyst and 450 mL of toluene to a butadiene polymerization reactor in the high-cis-butadiene rubber synthesis process at 45°C, add 350 g of butadiene, stir, and react for 1 hour to produce 38 g of polybutadiene with a cis content of 91% and a molecular weight of 150,000;

[0031] (2) The cis-butylene-styrene butadiene rubber solution was sent to the rubber solution storage tank, the storage tank was maintained at 45°C, stirred, and 40 mL of THF was added to the storage tank;

[0032] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 30 mL of styrene, 0.1 mL of 1.0 M butyl lithium, and 35 g of butadiene were added, stirred, and reacted at 45° C. for 2.5 hours.

[0033] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.2 mL of silicon tetrachloride was added. The polymerization temperature was 45° C. and the polymerization time was 1.5 hours.

[0034] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 46.5 g of butylene-butadiene styrene integrated rubber was obtained, and the styrene content in the product was 3.5%.

[0035] Example 2

[0036] (1) 0.11 g of cobalt naphthenate catalyst and 530 mL of toluene were added to a butadiene polymerization reactor in the high-cis-butadiene rubber synthesis process at 65° C., followed by 360 g of butadiene. The mixture was stirred and reacted for 2 hours to produce 72.5 g of polybutadiene with a cis content of 93% and a molecular weight of 175,000.

[0037] (4) The butylbenzene-butadiene rubber solution was sent to the rubber solution storage tank, the storage tank was maintained at 55°C, stirred, and 45 mL of ether was added to the storage tank;

[0038] (5) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 35 mL of styrene, 0.15 mL of 1.0 M butyl lithium, and 40 g of butadiene were added, stirred, and reacted at 55° C. for 3.5 hours.

[0039] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.22 mL of tin tetrachloride was added. The polymerization temperature was 55° C. and the polymerization time was 3 hours.

[0040] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 89.6 g of butylene-butadiene styrene integrated rubber was obtained, and the styrene content in the product was 2.5%.

[0041] Example 3

[0042] (1) Adding 0.11 g of nickel naphthenate catalyst, 550 mL of toluene and 150 mL of heptane to a butadiene polymerization reactor in a high-cis-butadiene rubber synthesis process at 35°C, charging 370 g of butadiene, stirring, heating to 70°C and reacting for 4 hours, to produce 87.5 g of polybutadiene with a cis content of 95% and a molecular weight of 216,000;

[0043] (2) The glue solution was sent to the glue solution storage tank, the storage tank was maintained at 55°C, stirred, and 50 mL of THF was added to the storage tank;

[0044] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 45 mL of styrene, 0.2 mL of 1.0 M butyl lithium, and 45 g of butadiene were added, stirred, and reacted at 55° C. for 5.5 hours.

[0045] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.25 mL of disiloxane hexachloride was added. The polymerization temperature was 55° C. and the polymerization time was 3.5 hours.

[0046] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 94.6 g of butylene-butadiene styrene integrated rubber was obtained, and the styrene content in the product was 3.3%.

[0047] Example 4

[0048] (1) Adding 0.15 g of neodymium naphthenate catalyst, 650 mL of toluene and 150 mL of heptane to a butadiene polymerization reactor in a high-cis-butadiene rubber synthesis process at 35° C., charging 380 g of butadiene, stirring, raising the temperature to 70° C. and reacting for 4.5 hours, to produce 121.6 g of polybutadiene with a cis content of 97% and a molecular weight of 268,000;

[0049] (2) The glue solution is sent to the glue solution storage tank, the storage tank is maintained at 50°C, stirred, and 40 mL of triethylamine is added to the storage tank;

[0050] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 80 mL of styrene, 0.3 mL of 1.0 M butyl lithium, and 65 g of butadiene were added, stirred, and reacted at 50° C. for 5 hours;

[0051] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.5 mL of tin tetrachloride was added. The polymerization temperature was 55° C. and the polymerization time was 5.5 hours.

[0052] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 134.8 g of butylene-butadiene styrene integrated rubber was obtained, and the styrene content in the product was 2.8%.

[0053] Example 5

[0054] (1) Adding 0.15 g of neodymium cyclohexane catalyst and 750 mL of benzene to a butadiene polymerization reactor in a high-cis-butadiene rubber synthesis process at 30° C., charging 380 g of butadiene, stirring, heating to 65° C., and reacting for 4.5 hours to produce 128.5 g of polybutadiene with a cis content of 97.5% and a molecular weight of 312,000;

[0055] (2) The glue solution is sent to the glue solution storage tank, the storage tank is maintained at 65°C, stirred, and 40 mL of butyl ether is added to the storage tank;

[0056] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 80 mL of styrene, 0.3 mL of 1.0 M butyl lithium, 65 g of butadiene, and 20 mL of isoprene were added, stirred, and reacted at 65° C. for 5 hours;

[0057] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.5 mL of tin tetrachloride was added. The polymerization temperature was 65° C. and the polymerization time was 6.5 hours.

[0058] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 161.5 g of butylene-butadiene styrene integrated rubber was obtained, wherein the styrene content of the product was 5.6% and the isoprene content was 1.5%.

[0059] Example 6

[0060] (1) Adding 0.15 g of neodymium naphthenate catalyst, 750 mL of toluene and 120 mL of octane to a butadiene polymerization reactor in a high-cis-butadiene rubber synthesis process at 30° C., charging 380 g of butadiene, stirring, heating to 85° C. and reacting for 4.5 hours, to produce 138.3 g of polybutadiene with a cis content of 97.5% and a molecular weight of 326,000;

[0061] (2) The glue solution was sent to the glue solution storage tank, the storage tank was maintained at 55°C, stirred, and 45 mL of THF was added to the storage tank;

[0062] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 80 mL of styrene, 0.5 mL of 1.0 M butyl lithium, 65 g of butadiene, and 40 mL of MMA were added, stirred, and reacted at 75° C. for 6 hours;

[0063] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.5 mL of tin tetrachloride was added. The polymerization temperature was 75° C. and the polymerization time was 6 hours.

[0064] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 183.6 g of butylene-butadiene styrene integrated rubber was obtained, with a styrene content of 3.6% and an MMA content of 3.8%.

[0065] Example 7

[0066] (1) Add 0.0025 g of dimethylsilyl-2,6-difluoroanilinocyclopentadiene titanium dichloride, 750 mL of toluene and 120 mL of heptane to the polymerization reactor of the POE synthesis process at 140°C, add 380 g of 1-octene, fill with ethylene to 4.0 MPa, stir, and react for 2 hours to produce 141.6 g of POE with a molecular weight of 186,000;

[0067] (2) The POE glue solution was sent to the glue solution storage tank, the storage tank was maintained at 85°C, stirred, and 46 mL of aniline was added to the storage tank;

[0068] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 80 mL of styrene, 0.5 mL of 1.0 M butyl lithium, 65 g of butadiene, and 40 mL of isoprene were added, stirred, and reacted at 85° C. for 6 hours.

[0069] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.5 mL of tin tetrachloride was added. The polymerization temperature was 85° C. and the polymerization time was 6 hours.

[0070] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 203.6 g of POE-styrene-butadiene integrated rubber was obtained, with a styrene content of 3.3% and an isoprene content of 3.1%.

[0071] Example 8

[0072] (1) Add 0.0025 g of 2,6-difluoroanilinocarbonyldimethylindene titanium dichloride, 750 mL of toluene, and 120 mL of heptane to the polymerization reactor of the EPDM synthesis process at 70°C, add 20 g of norbornene, add 1 kg of propylene, and charge ethylene to 4.0 MPa. Stir and react for 2 hours to produce 135.6 g of EPDM with a molecular weight of 388,000.

[0073] (2) The EPDM glue solution was sent to the glue solution storage tank, the storage tank was maintained at 70°C, stirred, and 46 mL of THF was added to the storage tank;

[0074] (3) The rubber solution was fed into the anionic polymerization process of styrene-butadiene rubber, and 80 mL of styrene, 0.5 mL of 1.0 M butyl lithium, 65 g of butadiene, and 40 mL of isopentene were added, stirred, and reacted at 70° C. for 6 hours;

[0075] (4) The rubber solution was fed into the post-polymerization reactor of the styrene-butadiene rubber anionic polymerization process, stirred, and 0.5 mL of tin tetrachloride was added. The polymerization temperature was 70° C. and the polymerization time was 6 hours.

[0076] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 153.8 g of EPDM-styrene-butadiene integrated rubber was obtained, with a styrene content of 5.6% and an isopentene content of 3.6%.

[0077] Example 9

[0078] (1) Add 0.0025 g of 2,6-difluoroanilinocarbonyldimethylindene titanium dichloride, 750 mL of toluene and 120 mL of heptane to the polymerization reactor of the POE synthesis process at 140°C, add 380 g of 1-octene, fill with ethylene to 4.0 MPa, stir, and react for 2 hours to produce 193.8 g of POE with a molecular weight of 219,000;

[0079] (2) The POE glue solution was sent to the glue solution storage tank, the storage tank was maintained at 85°C, stirred, and 35 mL of 4-fluoroaniline was added to the storage tank;

[0080] (3) The POE glue solution was fed into the styrene-butadiene acrylonitrile free radical polymerization process, 90 mL of styrene, 0.5 g of AIBN, and 100 g of acrylonitrile were added, stirred, and reacted at 85°C for 6 hours;

[0081] (4) The glue solution was fed into the post-polymerization reactor of the styrene-butadiene acrylonitrile free radical polymerization process, stirred, and 1.0 mL of tetrahydrofuran was added. The polymerization temperature was 85° C. and the polymerization time was 0.5 h.

[0082] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 246.6 g of POE-SAN integrated rubber was obtained, with a styrene content of 5.6% and an acrylonitrile content of 4.6%.

[0083] Example 10

[0084] (1) Adding 0.15 g of neodymium naphthenate catalyst, 750 mL of toluene and 120 mL of octane to a butadiene polymerization reactor in a high-cis-butadiene rubber synthesis process at 30° C., charging 380 g of butadiene, stirring, heating to 85° C. and reacting for 4.5 hours, to produce 138.3 g of polybutadiene with a cis content of 97.5% and a molecular weight of 326,000;

[0085] (2) The glue solution is sent to the glue solution storage tank, the storage tank is maintained at 55°C, stirred, and 45 mL of dioxane is added to the storage tank;

[0086] (3) The glue solution was sent to the styrene-butadiene acrylonitrile free radical polymerization process, 90 mL of styrene, 0.5 g of AIBN, and 100 g of acrylonitrile were added, stirred, and reacted at 85°C for 5 hours;

[0087] (4) The glue solution was fed into the post-polymerization reactor of the styrene-butadiene acrylonitrile free radical polymerization process, stirred, and 1.0 mL of tetrahydrofuran was added. The polymerization temperature was 85° C. and the polymerization time was 0.5 h.

[0088] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 146.6 g of butyl-SAN integrated rubber was obtained, with a styrene content of 5.2% and an acrylonitrile content of 4.6%.

[0089] Example 11

[0090] (1) Adding 0.15 g of neodymium naphthenate catalyst, 750 mL of toluene and 120 mL of octane to a butadiene polymerization reactor in a high-cis-butadiene rubber synthesis process at 30° C., charging 380 g of butadiene, stirring, heating to 85° C. and reacting for 4.5 hours, to produce 138.3 g of polybutadiene with a cis content of 97.5% and a molecular weight of 326,000;

[0091] (2) The glue solution was fed into a glue solution storage tank, maintained at 110°C, stirred, and 150 mL of toluene was added to the tank; (3) The glue solution was fed into a styrene-butadiene polymerization process to synthesize POE, 0.0025 g of 2,6-difluoroanilinocarbonyldimethylindene titanium chloride was added, 90 mL of 1-octene was added, ethylene was introduced to a pressure of 3 MPa, stirred, and reacted at 110°C for 0.5 hours;

[0092] (4) The glue solution was fed into the post-polymerization reactor of the styrene-butadiene polymerization process, stirred, and 5 mL of ethanol was added. The polymerization temperature was 55°C and the polymerization time was 0.5 hours.

[0093] (5) After flash evaporation, coagulation, dehydration, drying, and packaging, 216.6 g of butadiene-polyethylene glycol (POE) integrated rubber and 21.6% of 1-octene were obtained.

Claims

1. A method for preparing a butadiene-styrene-butadiene integrated rubber, characterized in that: The cis-butadiene-styrene integrated rubber is a high cis polybutadiene rubber polybutadiene rubber synthesized by in-situ anionic polymerization of high cis polybutadiene rubber and butadiene styrene; wherein the high cis polybutadiene rubber is synthesized by coordination polymerization of butadiene catalyzed by a catalyst, and the cis content is higher than 90%, and the catalyst is a titanium catalyst, a cobalt catalyst, a nickel catalyst or a rare earth catalyst; wherein the polybutadiene rubber is prepared by anionic polymerization of butadiene, styrene and polybutadiene rubber initiated by an anionic polymerization initiator; wherein the The anionic polymerization initiator is a monolithium initiator, a dilithium initiator, a sodium initiator or a potassium initiator; the mass ratio of the high cis polybutadiene rubber to the polystyrene butadiene rubber is 1:(0.05-95); the cis content of butadiene in the polystyrene butadiene rubber is 3-35%, the trans content of butadiene is 2-55%, the vinyl content is 2-57%, and the styrene content is 1-30%; the weight average molecular weight of the polystyrene butadiene rubber is 0.5-1 million, the molecular weight distribution (PDI) is less than 2, and the conversion rate of styrene is greater than 60%.

2. The method for preparing the butadiene-styrene integrated rubber according to claim 1, wherein: One or more storage tanks are added after the post-polymerization reactor of the synthesis reactor of the high-cis polybutadiene rubber synthesis process, the temperature is maintained constant and stirring is carried out to terminate the coordination polymerization reaction of butadiene, and then the butadiene styrene solution anion polymerization process is connected, styrene and anionic initiator are added, butadiene is replenished, and a polarity regulator is added to cause butadiene styrene to undergo anionic polymerization, and a butadiene styrene-polybutadiene rubber copolymer is generated in situ in the high-cis polybutadiene rubber solution. A chain extender is added to the last polymerization reactor of the anionic polymerization process to prepare a cis-butylene-butadiene styrene integrated rubber, wherein the chain extender is selected from silicon tetrachloride, tin tetrachloride or disilane hexachloride.

3. The method for preparing the butadiene-styrene integrated rubber according to claim 1, wherein: The high-cis polybutadiene rubber synthesis process adopts coordination polymerization to synthesize high-cis polybutadiene rubber; in the butadiene styrene anionic polymerization process, anionic copolymerization reaction occurs with the double-bonded polybutadiene rubber molecules produced in the high-cis polybutadiene rubber synthesis process, thereby realizing the cis-butadiene-butadiene integrated rubber in which the polybutadiene rubber molecules and the styrene-butadiene rubber molecules are connected by chemical bonds.

4. The method for preparing the butadiene-styrene integrated rubber according to claim 1, wherein: The integrated butadiene-styrene rubber preparation process is as follows: one or more rubber storage tanks are added after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis process, and the storage tanks are connected to the butadiene-styrene rubber anion polymerization process; wherein the high-cis polybutadiene rubber synthesis process is composed of 1-5 polymerization kettles; wherein the storage tank is used to add a terminator to terminate the coordination polymerization reaction of butadiene, and styrene, anionic initiator, butadiene supplement, and polarity regulator are added to the same storage tank; wherein the butadiene-styrene rubber anion polymerization process is composed of 1-3 polymerization kettles, and a chain extender is added to the post-polymerization kettle of the butadiene-styrene rubber anion polymerization process; wherein the integrated butadiene-styrene rubber preparation process is a continuous process, a semi-continuous process, or a batch process.

5. The method for preparing the butadiene-styrene integrated rubber according to claim 1, wherein: The synthesis process of high cis-polybutadiene rubber is composed of 1-5 polymerization kettles, the polymerization reaction time is 0.5-8 hours, the polymerization reaction temperature is 30-200℃, the pressure of the polymerization kettle is 0.1-1MPa, and the inert organic solvent is C5-C 20 The organic solvent is selected from benzene, toluene, hexane, heptane, cyclohexane or a mixed solvent thereof, the cis content of butadiene in the high cis-butadiene rubber is higher than 90%, the Mooney viscosity is 30-55, and the weight average molecular weight is 0.5-600,000; wherein the anionic polymerization process of the styrene-butadiene rubber is composed of 1-3 polymerization kettles, the polymerization temperature is 30-180°C, the polymerization time is 0.5-8 hours, and the polymerization pressure is 0.2-5.0 MPa, the cis content of butadiene in the styrene-butadiene rubber is 3-35%, the trans content of butadiene is 2-55%, the vinyl content is 2-57%, and the styrene content is 1-30%, the weight average molecular weight of the styrene-butadiene rubber is 0.5-1 million, the molecular weight distribution PDI is less than 2, and the conversion rate of styrene is greater than 60%.

6. The method for preparing butadiene-styrene integrated rubber according to claim 1, wherein: The process is as follows: (1) adding butadiene, toluene and catalyst from a monomer butadiene preparation tank, an inert organic solvent toluene preparation tank and a catalyst preparation tank respectively into a butadiene polymerization kettle of a high cis-butadiene rubber synthesis process, wherein the weight ratio of butadiene to catalyst is 20000:(0.1-10), and the weight ratio of toluene to butadiene is 1:(0.3-1.5); the polymerization reaction time is 0.5-8 hours, the polymerization reaction temperature is 30-200°C, the pressure of the polymerization kettle is 0.1-5MPa, the conversion rate of butadiene is 30-90%, the cis content of polybutadiene is higher than 90%, the Mooney viscosity is 30-55, and the weight average molecular weight is 0.5-600,000; the catalyst is a titanium catalyst, a cobalt catalyst, a nickel catalyst or a rare earth catalyst; (2) Send the butadiene-styrene butadiene rubber solution into the rubber solution storage tank, maintain the storage tank at 30-180℃, stir, and add C2-C 20 Organic compounds containing heteroatoms adjust the polarity of the solvent and terminate the active centers of butadiene coordination polymerization; (3) the rubber solution is fed into the anionic polymerization process of styrene-butadiene rubber, styrene is added from the styrene preparation tank, initiator is added from the anionic polymerization initiator preparation tank, and butadiene is added from the butadiene preparation tank. The weight ratio of styrene to initiator is 50,000:(0.1-10), and the weight ratio of butadiene to initiator is 50,000:(0.1-10). The polymerization temperature is 30-180° C., the polymerization time is 0.5-8 hours, and the polymerization pressure is 0.2-5.0 MPa. The styrene-butadiene rubber has a cis content of butadiene of 3-35%, a trans content of butadiene of 2-55%, a vinyl content of 2-57%, and a styrene content of 1-30%. The weight average molecular weight of the styrene-butadiene rubber is 0.5-1,000,000, the molecular weight distribution (PDI) is less than 2, and the conversion rate of styrene is greater than 60%. (4) the rubber solution is fed into the post-polymerization reactor of the anionic polymerization process of styrene-butadiene rubber, stirred, and a chain extender is added. The polymerization temperature is 30-180° C., the polymerization time is 0.5-8 hours, and the polymerization pressure is 0.2-5.0 MPa; the chain extender is silicon tetrachloride, tin tetrachloride, or disilane hexachloride; (5) obtaining butadiene-styrene-butadiene integrated rubber through flash evaporation, coagulation, dehydration, drying, and packaging; The catalyst is a titanium catalyst, a cobalt catalyst, a nickel catalyst or a rare earth catalyst, the titanium catalyst is titanium naphthenate, titanium tetrachloride, dimethylsilyl-2,6-difluoroanilinocyclopentadiene titanium dichloride or 2,6-difluoroanilinocarbon-dimethylindene titanium dichloride, the cobalt catalyst is cobalt naphthenate, the nickel catalyst is nickel naphthenate, the rare earth catalyst is neodymium naphthenate, 2,6-difluoroanilinocarbon-dimethylindene neodymium chloride, cerium naphthenate, scandium naphthenate, samarium naphthenate or yttrium naphthenate; the anionic polymerization initiator is a monolithium initiator, a dilithium initiator, a sodium initiator or a potassium initiator; the C2-C 20 The organic compound containing heteroatoms is THF, ether, butyl ether, dioxane, triethylamine, aniline, fluoroaniline or a mixture thereof; wherein the inert organic solvent is C5-C 20 The organic matter is selected from benzene, toluene, hexane, heptane, cyclohexane or a mixed solvent thereof.

7. The method for preparing the butadiene-styrene integrated rubber according to claim 1, wherein: A preparation method for an integrated material of two or more other rubbers or two or more other resins or two or more other fibers, wherein a storage tank is added after the EPDM post-polymerization kettle, the temperature is maintained constant, stirring is carried out, the coordination polymerization reaction of EPDM is terminated, and then the butadiene styrene solution anion polymerization process is connected, or any other solution polymerization process is connected to prepare EPDM and styrene butadiene rubber integrated rubber; a storage tank is added after the POE polymerization kettle, the operating temperature of the anion polymerization process is maintained constant, stirring is carried out, the coordination polymerization reaction of POE is terminated, and then the butadiene styrene solution anion polymerization process is connected, or any other solution polymerization process is connected to prepare EPDM and styrene butadiene rubber integrated rubber. process to prepare POE elastomer styrene butadiene rubber integrated rubber; a storage tank is added after the post-polymerization kettle of the high-cis polybutadiene rubber synthesis kettle to maintain the operating temperature of the free radical polymerization process unchanged and stir, and then connect the acrylonitrile styrene melt method or solution method free radical polymerization process to produce high-cis butadiene rubber and SAN resin integrated rubber and plastic materials; a storage tank is added after the POE polymerization kettle to maintain the operating temperature of the melt method free radical polymerization process unchanged and stir, terminate the coordination polymerization reaction of POE, and then connect the butadiene acrylonitrile melt method or solution method free radical polymerization process, or connect any other solution polymerization process to produce POE elastomer nitrile butadiene rubber integrated rubber.

8. The butadiene-styrene-butadiene integrated rubber prepared by any one of the methods described in claims 1 to 7.

9. Use of the butadiene-styrene integrated rubber according to claim 8.