A heat-resistant anti-oxidative aging trans rubber alloy material, its preparation method and uses

Abstract

The present invention discloses a trans rubber alloy material and its preparation and application. The trans rubber alloy of the present invention is prepared by block copolymerization or parallel polymerization of butadiene and isoprene. By adjusting the process parameters of block copolymerization, including the monomer ratio and hydrogen dosage in different reaction stages, a trans rubber alloy material composed of three copolymers, namely 40-80% by mass of butadiene-isoprene random copolymer, 15-45% by mass of butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block, 5-15% by mass of butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block, as well as fillers and additives, etc., is obtained. This trans rubber alloy has excellent comprehensive mechanical properties, tear resistance, high strength, high modulus and high-temperature dynamic fatigue properties, and is suitable for making long-life tires and vibration damping products.

Description

Technical Field

[0001] The invention belongs to the field of synthetic rubber, in particular to the field of rubber synthesis and process technology, and more particularly to a preparation method of a trans rubber alloy and the structural composition of the trans rubber alloy. Background Art

[0002] Trans-1,4-structured diene polymers, such as high trans-1,4-polyisoprene (TPI) and high trans-1,4-polybutadiene (TPB), have excellent flexural resistance, low rolling resistance, and low compression heat generation, and can be used as environmentally friendly high-performance rubber materials for automotive tires, which has gradually attracted people's attention. However, due to crystallization, TPI and TPB are crystalline plastics at room temperature, which are difficult to process with conventional rubber processing methods, and their application is limited.

[0003] The main methods for destroying the crystallinity of TPI or TPB include physical methods and chemical methods. Among them, copolymerization in the chemical method is an effective way to break the crystallinity by using two monomer units of butadiene and isoprene with different molecular structures to interpenetrate each other in the polymer molecular chain during polymerization to change the regularity of the molecular chain. Chinese invention patent CN102086277 discloses two different catalyst systems to initiate isoprene polymerization to obtain isoprene homopolymers with trans structure and 3,4-structure. Chinese invention patents CN 105754023, 102050968, 114369294, 114349904, etc. respectively use isoprene or butadiene to homopolymerize first to obtain active granular homopolymer TPI or TPB, and then copolymerize butadiene and isoprene to obtain trans-butylene-pentadiene copolymer rubber TBIR, or first copolymerize the two monomers, and use the difference in the reactivity rate of the two monomers to form isoprene homopolymerization to obtain homopolymerized isoprene homopolymer TPI when the conversion rate is increased in the later stage. In the above publicly reported polymers, due to the limitation of the polymerization process, there are a large number of TPI or TPB homopolymers, which still have the disadvantage of being unable to be processed and applied normally. Chinese invention patents CN 107686536, 105601814, 103387641, 103204973, etc. respectively disclose the process of adding two monomers together for copolymerization and the industrial polymerization process of copolymer rubber, to obtain copolymers with uniform composition or copolymers whose composition changes with conversion rate or gradient. However, the microstructure parameters such as butadiene content in the above publicly reported products change irregularly with conversion rate, so it is impossible to accurately control the microstructure composition from the perspective of process parameters. Chinese invention patent CN110563870 reports the rubber synthesis process, but does not involve how to add. It is a process in which a horizontal reactor is used as a special polymerization equipment. Summary of the invention

[0004] In view of the problems existing in the above-mentioned prior art solutions, the object of the present invention is to provide a preparation method of a trans rubber alloy material. Specifically, by designing a novel polymerization process and controlling the innovative polymerization condition parameters, the design and synthesis of the microstructure of the product are realized.

[0005] Based on the above preparation method, another object of the present invention is to provide a trans rubber alloy material with multiple components and adjustable structures of each component. To achieve the first object of the present invention, the following steps are designed:

[0006] (1) Add a predetermined amount of inert solvent, butadiene, isoprene, co-initiator, main initiator and hydrogen to the pre-treated polymerization reactor in sequence. The molar ratio of titanium element in the main initiator to the monomer is 0.001×10 -5 ~10×10 -5 :1, the molar ratio of aluminum element in the co-initiator to titanium element in the main initiator is 10~400:1, the molar ratio of butadiene to isoprene is 8~15:100, the volume ratio of inert solvent to monomer is 0~400:100, the molar ratio of hydrogen to monomer is 1:200~1500, the polymerization temperature is 20~80°C, and the polymerization time is 0.1~6 hours. Carry out the copolymerization of butadiene and isoprene to obtain a trans-1,4-structured butadiene-isoprene random copolymer.

[0007] (2) When the polymerization time of the above system reaches any time point within 0.1~6 hours, add isoprene and hydrogen to the polymerization system, so that the molar ratio of butadiene to isoprene in the polymerization system is 0.1~7:100, the molar ratio of hydrogen to monomer is 1:200~800, the polymerization reaction temperature is 20~80°C, and the polymerization time is 0.1~6 hours. Polymerize to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene (TPI) block.

[0008] (3) When the polymerization time of the above system reaches any time point within 0.1~6 hours, add inert solvent, butadiene and hydrogen to the polymerization system, so that the molar ratio of butadiene to isoprene in the polymerization system is 30~80:100, the volume ratio of inert solvent to monomer is 0~200:100, the molar ratio of hydrogen to monomer is 1:30~400, the polymerization reaction temperature is 20~100°C, and the polymerization time is 0.1~3 hours. Polymerize to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene (TPB) block.

[0009] (4) When the above polymerization time reaches any time point within 0.1 to 3 hours, isoprene and hydrogen are added to the polymerization system, such that the molar ratio of butadiene to isoprene in the polymerization system is 0.1 to 7:100, the molar ratio of hydrogen to monomers is 1:200 to 800, the polymerization reaction temperature is 20 to 80 °C, and the polymerization time is 0.1 to 3 hours, to obtain a butadiene-isoprene copolymer containing a longer TPI block;

[0010] (5) Steps (3) and (4) are repeated until the total polymerization time reaches 1 to 24 hours. The above materials enter the termination reactor, and a terminator, a chelating agent, an antioxidant, a filler, and other additives are added to terminate the polymerization reaction and disperse the additives and the filler. The temperature of the termination reactor is 30 to 90 °C, and the stirring time is 0.5 to 5 hours. Subsequently, volatile components are removed under vacuum, and extrusion granulation is performed to obtain a trans rubber alloy pellet composed of a butadiene-isoprene random copolymer with a trans-1,4 structure, a butadiene-isoprene copolymer containing a longer TPI block, and a butadiene-isoprene copolymer containing a longer TPB block.

[0011] To achieve the first object of the present invention, the present invention can also be carried out through the following steps:

[0012] (1) A predetermined amount of an inert solvent, butadiene, isoprene, a co-initiator, a main initiator, and hydrogen are sequentially added to a pre-treated polymerization reactor I. The molar ratio of titanium element in the main initiator to monomers is 0.001×10 -5 ~10×10 -5 :1, the molar ratio of aluminum element in the co-initiator to titanium element in the main initiator is 10 to 400:1, the molar ratio of butadiene to isoprene is 8 to 15:100, the volume ratio of the inert solvent to monomers is 0 to 200:100, the molar ratio of hydrogen to monomers is 1:200 to 1500, the polymerization temperature is 20 to 80 °C, and the polymerization time is 0.1 to 6 hours, to obtain a butadiene-isoprene random copolymer;

[0013] (2) A predetermined amount of an inert solvent, butadiene, isoprene, a co-initiator, a main initiator, and hydrogen are sequentially added to a pre-treated polymerization reactor II. The molar ratio of titanium element in the main initiator to monomers is 0.001×10 -5 ~10×10 -5 :1, the molar ratio of aluminum element in the co-initiator to titanium element in the main initiator is 10 to 400:1, the molar ratio of butadiene to isoprene is 0.1 to 7:100, the volume ratio of the inert solvent to monomers is 0 to 200:100, the molar ratio of hydrogen to monomers is 1:200 to 800, the polymerization temperature is 20 to 80 °C, and the polymerization time is 0.1 to 6 hours, to carry out the copolymerization of butadiene and isoprene, to obtain a butadiene-isoprene copolymer containing a longer TPI block;

[0014] (3) Sequentially add a predetermined amount of inert solvent, butadiene, isoprene, co-initiator, main initiator, and hydrogen into the pre-treated polymerization reactor III. The molar ratio of titanium element in the main initiator to the monomers is 0.001×10 -5 ~10×10 -5 :1. The molar ratio of aluminum element in the co-initiator to the titanium element in the main initiator is 10~400:1. The molar ratio of butadiene to isoprene is 30~80:100. The volume ratio of the inert solvent to the monomers is 0~200:100. The molar ratio of hydrogen to the monomers is 1:30~400. The polymerization temperature is 20~100 °C, and the polymerization time is 0.1~3 hours. Carry out the copolymerization of butadiene and isoprene to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene (TPB) block;

[0015] (3) Transfer the materials in the above three reactors to the termination reactor IV. Add a terminator, a chelating agent, an antioxidant, a filler, and other additives to the termination reactor IV to terminate the polymerization reaction and disperse the additives and the filler. The reactor temperature is 30~90 °C, and the stirring time is 0.5~5 hours. Subsequently, remove the volatile components under vacuum and extrude and pelletize to obtain a trans rubber alloy pellet composed of a butadiene-isoprene random copolymer with a trans-1,4 structure, a butadiene-isoprene copolymer containing a longer TPI block, and a butadiene-isoprene copolymer containing a longer TPB block.

[0016] In the preparation method of the present invention, batch polymerization or continuous polymerization is adopted; the polymerization reactor is one or two of a kettle reactor, a fluidized bed reactor, a tubular reactor, or a horizontal reactor in parallel or in series; the termination reactor is a horizontal reactor or a single use of a screw reactor or a series use of both.

[0017] The main initiator used in the present invention is a supported titanium catalyst, in which the titanium element accounts for 1%~5% of the total mass of the supported catalyst, and is one of titanium tetrachloride, titanium tetrabromide, or titanium tetraiodide; the internal electron donor accounts for 0.01%~20% of the total mass of the supported catalyst, and is one or more of benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, phenylacetic acid, diisobutyl phthalate, dibutyl phthalate, benzoquinone, methyl benzoate, ethyl benzoate, 9,9-bis(methoxymethyl)fluorene; the support is one of magnesium dichloride, magnesium dibromide, or magnesium diiodide.

[0018] The co-initiators used in the present invention are one or two or more of triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, methylaluminum dichloride, sesquialethylaluminum chloride, diethylaluminum chloride, monoethylaluminum dichloride, diisobutylaluminum chloride, mono-isobutylaluminum dichloride, sesquisisobutylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride; the inert solvent is one or two of hydrogenated gasoline, gasoline, hexane, heptane, benzene, toluene, xylene.

[0019] In the preparation method of the present invention, the terminator used is one of water, ethanol, propanol, butanol, and the mass ratio of the terminator to the trans rubber alloy is 0.1-4:100; the anti-aging agent is one or two of phenolic anti-aging agents, amine anti-aging agents, phosphite anti-aging agents, thioester anti-aging agents, and the mass ratio of the anti-aging agent to the trans rubber alloy is 0.1-4:100.

[0020] In the preparation method of the present invention, a chelating agent is particularly used to adjust the microstructure of the polymer. The chelating agent is one or several of ethylenediaminetetraacetate, ethylenediaminetriaminepentaacetate, nitrilotriacetic acid disodium, oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, citrate, tartrate, gluconate, benzotriazole, guanidine derivatives, hydroxyethylidene-1,1-diphosphonate, aminotrimethylenephosphonate, diethylenetriaminepenta(methylene phosphonic acid), triethylenetetraminehexa(methylene), bis(1,6-hexylene)triaminepenta(methylene phosphonic acid), polyamino polyether tetra(methylene phosphonic acid), polyvinyl alcohol, polyethylene glycol, polymethacryloylacetone, polyacryloylacetone, vinyl acetate-acryloyl acetoacetate copolymer, polyaniline, polydopamine, styrene-maleic anhydride copolymer, polyurethane elastomer, polyether elastomer, etc., and the mass ratio of the chelating agent to the trans rubber alloy is 0.1-4:100.

[0021] In the present invention, the filler is one or two of carbon blacks and silica of various models, and the mass ratio of the filler to the trans rubber alloy is 0-100:100; the other additives are one or more of zinc oxide, magnesium oxide, and coupling agent. The mass ratio of the zinc oxide to the trans rubber alloy is 0-6:100; the mass ratio of the magnesium oxide to the trans rubber alloy is 0-6:100; the mass ratio of the coupling agent to the trans rubber alloy is 0-10:100. By the preparation method of the present invention, the second object of the present invention is achieved, that is, a novel trans-butadiene-pentene copolymer rubber alloy is obtained. The trans rubber alloy of the present invention comprises a random copolymer of butadiene-isoprene (G fraction) with a mass fraction of 40-80%, a butadiene-isoprene copolymer (F fraction) containing a longer trans-1,4-polyisoprene (TPI) block with a mass fraction of 15-45%, a butadiene-isoprene copolymer (A fraction) containing a longer trans-1,4-polybutadiene (TPB) block with a mass fraction of 5-15%, and well-dispersed filler, chelating agent, anti-aging agent, zinc oxide, magnesium oxide, and coupling agent.

[0022] The trans rubber alloy of the present invention comprises a random copolymer of butadiene-isoprene (G fraction) with a mass fraction of 40-80%, a butadiene-isoprene copolymer (F fraction) containing a longer trans-1,4-polyisoprene block with a mass fraction of 15-45%, and a butadiene-isoprene copolymer (A fraction) containing a longer trans-1,4-polybutadiene block with a mass fraction of 5-15%; the trans-1,4-structure content of the copolymer is greater than 90%.

[0023] In the trans rubber alloy of the present invention, the molar content of butadiene units in the random copolymer (G fraction) is 21-35%, and the crystallization melting temperature is -20-20°C; the molar content of butadiene units in the copolymer (F fraction) is 5-20%, and the crystallization melting temperature is 20-55°C; the molar content of butadiene units in the copolymer (A fraction) is 36-90%, the crystallization transition temperature is 60-75°C, and the crystallization melting temperature is 120-145°C; the trans-1,4-structure content of the copolymer is greater than 90%, and the weight-average molecular weight is 300,000-1.2 million.

[0024] The special feature of the present invention lies in that the trans rubber alloy material of the present invention has good heat aging resistance. In the trans-butadiene-pentene copolymer alloy, the G fraction is a random copolymer of butadiene-isoprene with a trans-1,4 structure, providing excellent comprehensive properties; the A fraction is a butadiene-isoprene copolymer containing a long trans-1,4-polybutadiene block, providing a high melting point TPB nanosheet crystal structure; the F fraction is a butadiene-isoprene copolymer containing a long trans-1,4-polyisoprene block, providing a low melting point nanosheet crystal structure. The A fraction and the F fraction together contribute high strength, high modulus and excellent high temperature dynamic fatigue performance to the trans rubber alloy, and are applied to the tread rubber and sidewall rubber of truck tires, car tires, giant tires, and rubber vibration damping products, which can significantly improve the dynamic fatigue life of the products. Detailed implementation mode

[0025] The following will further elaborate on the present invention in combination with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and do not limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0026] Unless otherwise specified, the methods and equipment used in the present invention are conventional methods and equipment in the art.

[0027] Example 1

[0028] After treating a 3L polymerization kettle with vacuum nitrogen, add butadiene, isoprene, triisobutylaluminum, magnesium dichloride supported titanium catalyst (titanium loading 2wt%), and hydrogen to the polymerization kettle in sequence according to the parameters in Table 1. Set the reaction temperature of the polymerization kettle at 30°C and carry out the first-stage polymerization for 2.5 hours. Subsequently, supplement isoprene and hydrogen to the polymerization system according to the parameters in Table 1, control the polymerization temperature at 30°C, and carry out the second-stage polymerization for 2 hours. Subsequently, supplement butadiene and hydrogen to the polymerization system according to the parameters in Table 1, control the polymerization temperature at 30°C, and carry out the third-stage polymerization for 1 hour. Repeat the second-stage and third-stage polymerizations until the total reaction time reaches more than 15 hours, then transfer the polymerization system to the termination reactor, add 1g of terminator alcohol, 1g of antioxidant 264, and 2g of chelating agent N,N'-bis(2-hydroxybenzylidene)oxalyl dihydrazide, stir at 30°C for 0.5 hours, then add 300g of white carbon black and continue to stir for 1 hour. Subsequently, use vacuum decompression to remove unreacted monomers, solvents, hydrogen and other volatile substances, and extrude and granulate to obtain trans rubber alloy pellets. The polymerization parameters and polymer structure performance test data are shown in Table 1.

[0029] Example 2

[0030] After subjecting three 100 L stirred polymerization reactors connected in parallel to vacuum nitrogen treatment, the three reactors were charged respectively according to the three-stage polymerization process parameters in Table 1, while controlling the polymerization temperature at 30°C and reacting for 2 hours. Subsequently, the polymerization system was transferred to a termination reactor and stirred and mixed for 0.5 hours at a temperature of 30°C. Then, 2 g of terminator alcohol, 1 g of antioxidant 2264, and 2 g of chelating agent disodium ethylenediaminetetraacetate were added to the termination reactor, and the mixture was stirred for 0.5 hours at 30°C. Then, 250 g of carbon black was added and stirring continued for 1 hour. Subsequently, unreacted monomers, solvents, hydrogen and other volatile substances were removed by vacuum decompression, and extrusion granulation was carried out to obtain trans rubber alloy pellets. The polymerization parameters and polymer structure performance test data are shown in Table 1.

[0031] Example 3

[0032] Except that the polymerization parameters were in accordance with the data in Table 1, other steps were the same as in Example 2. The polymerization parameters and polymer structure performance test data are shown in Table 1.

[0033] Table 1 Main process parameters of Examples 1 - 3 and physical properties of the polymers prepared

[0034]

[0035]

Claims

1. A heat-resistant and oxygen-aging-resistant trans rubber alloy material, characterized in that, The trans rubber alloy is composed of a random copolymer of trans-1,4-structure butadiene-isoprene with a mass fraction of 40-80%, a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block with a mass fraction of 15-45%, a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block with a mass fraction of 5-15%, and well-dispersed fillers, chelating agents, antioxidants, zinc oxide, magnesium oxide, and coupling agents. The molar content of butadiene units in the random copolymer is 21-35%, and the crystallization melting temperature is -20-20 o °C. The molar content of butadiene units in the butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block is 5-20%, and the crystallization melting temperature is 20-55 o °C. The molar content of butadiene units in the butadiene-isoprene copolymer containing a longer trans-1,4-butadiene block is 36-90%, and the crystallization transition temperature is 60-75 o °C, and the crystallization melting temperature is 120-145 o °C. The content of trans-1,4-structure in the copolymer is greater than 90%, and the weight-average molecular weight is 300,000-1.2 million.

2. A preparation method of a heat-resistant and oxygen-aging-resistant trans rubber alloy material, characterized in that, Adopt the following method: Method 1 includes the following steps: (1) Add a predetermined amount of an inert solvent, butadiene, isoprene, a co-initiator, a main initiator, and hydrogen to a pre-treated polymerization reactor in sequence. The molar ratio of titanium element in the main initiator to the monomers is 0.001×10 -5 ~10×10 -5 :

1. The molar ratio of aluminum element in the co-initiator to titanium element in the main initiator is 10~400:

1. The molar ratio of butadiene to isoprene is 8~15:

100. The volume ratio of the inert solvent to the monomers is 0~400:

100. The molar ratio of hydrogen to the monomers is 1:200~1500. The polymerization temperature is 20~80°C, and the polymerization time is 0.1~6 hours. Carry out the copolymerization of butadiene and isoprene to obtain a trans-1,4-structured butadiene-isoprene random copolymer; (2) When the polymerization time of the above system reaches any time point within 0.1 - 6 hours, isoprene and hydrogen are added to the polymerization system, so that the molar ratio of butadiene to isoprene in the polymerization system is 0.1 - 7:100, the molar ratio of hydrogen to monomers is 1:200 - 800, the polymerization reaction temperature is 20 - 80 °C, and the polymerization time is 0.1 - 6 hours, to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block; (3) When the polymerization time of the above system reaches any time point within 0.1 - 6 hours, an inert solvent, butadiene, and hydrogen are added to the polymerization system, so that the molar ratio of butadiene to isoprene in the polymerization system is 30 - 80:100, the volume ratio of the inert solvent to monomers is 0 - 200:100, the molar ratio of hydrogen to monomers is 1:30 - 400, the polymerization reaction temperature is 20 - 100 °C, and the polymerization time is 0.1 - 3 hours, to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block; (4) When the above polymerization time reaches any time point within 0.1 - 3 hours, isoprene and hydrogen are added to the polymerization system, so that the molar ratio of butadiene to isoprene in the polymerization system is 0.1 - 7:100, the molar ratio of hydrogen to monomers is 1:200 - 800, the polymerization reaction temperature is 20 - 80 °C, and the polymerization time is 0.1 - 3 hours, to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block; (5) Repeat steps (3) and (4) until the total polymerization time reaches 1 - 24 hours. The above materials enter the termination reactor, and a terminator, a chelating agent, an antioxidant, a filler, and other additives are added to terminate the polymerization reaction and disperse the additives and the filler. The temperature of the termination reactor is 30 - 90 °C, and the stirring time is 0.5 - 5 hours. Subsequently, volatile components are removed under vacuum, and extrusion granulation is carried out to obtain trans rubber alloy pellets composed of a butadiene-isoprene random copolymer with a trans-1,4 structure, a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block, and a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block; Or Method 2 includes the following steps: (1) Add a predetermined amount of inert solvent, butadiene, isoprene, co-initiator, main initiator, and hydrogen into the pre-treated polymerization reactor I in sequence. The molar ratio of titanium element in the main initiator to the monomers is 0.001×10 -5 ~10×10 -5 :

1. The molar ratio of aluminum element in the co-initiator to titanium element in the main initiator is 10~400:

1. The molar ratio of butadiene to isoprene is 8~15:

100. The volume ratio of the inert solvent to the monomers is 0~200:

100. The molar ratio of hydrogen to the monomers is 1:200~1500. The polymerization temperature is 20~80°C, and the polymerization time is 0.1~6 hours to obtain a trans-1,4-structured butadiene-isoprene random copolymer; (2) Add a predetermined amount of inert solvent, butadiene, isoprene, co-initiator, main initiator and hydrogen to the pre-treated polymerization reactor II in sequence. The molar ratio of titanium element in the main initiator to the monomers is 0.001×10 -5 ~10×10 -5 :

1. The molar ratio of aluminum element in the co-initiator to the titanium element in the main initiator is 10~400:

1. The molar ratio of butadiene to isoprene is 0.1~7:

100. The volume ratio of the inert solvent to the monomers is 0~200:

100. The molar ratio of hydrogen to the monomers is 1:200~800. The polymerization temperature is 20~80 °C and the polymerization time is 0.1~6 hours. Carry out the copolymerization of butadiene and isoprene to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block; (3) Add a predetermined amount of inert solvent, butadiene, isoprene, co-initiator, main initiator, and hydrogen to the pre-treated polymerization reactor III in sequence. The molar ratio of titanium element in the main initiator to the monomer is 0.001×10 -5 ~10×10 -5 :

1. The molar ratio of aluminum element in the co-initiator to the titanium element in the main initiator is 10~400:

1. The molar ratio of butadiene to isoprene is 30~80:

100. The volume ratio of the inert solvent to the monomer is 0~200:

100. The molar ratio of hydrogen to the monomer is 1:30~400. The polymerization temperature is 20~100 °C, and the polymerization time is 0.1~3 hours. Carry out the copolymerization of butadiene and isoprene to obtain a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block; (3) The materials in the above three reactors are transported to the termination reactor IV, and a terminator, a chelating agent, an antioxidant, a filler, and other additives are added to the termination reactor IV to terminate the polymerization reaction and disperse the additives and the filler. The reactor temperature is 30 - 90 °C, and the stirring time is 0.5 - 5 hours. Subsequently, volatile components are removed under vacuum, and extrusion granulation is carried out to obtain trans rubber alloy pellets composed of a butadiene-isoprene random copolymer with a trans-1,4 structure, a butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block, and a butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block.

3. The preparation method according to claim 2, characterized in that, The polymerization reactor is one or two of a kettle reactor, a fluidized bed reactor, a tubular reactor or a horizontal reactor in parallel or series; the termination reactor is a single use of a horizontal reactor or a screw reactor or a series use of both.

4. The preparation method according to claim 2, wherein The main initiator is a supported titanium catalyst, in which titanium accounts for 1% - 5% of the total mass of the supported catalyst, and is one of titanium tetrachloride, titanium tetrabromide or titanium tetraiodide; the internal electron donor accounts for 0.01% - 20% of the total mass of the supported catalyst, and is one or more of benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, phenylacetic acid, diisobutyl phthalate, dibutyl phthalate, benzoquinone, methyl benzoate, ethyl benzoate, 9,9-bis(methoxymethyl)fluorene; the support is one of magnesium dichloride, magnesium dibromide, magnesium diiodide as the carrier; the co-initiator is one or a combination of two or more of triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, methylaluminum dichloride, sesquialethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, sesquisisobutylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride; the inert solvent is one or two of hydrogenated gasoline, gasoline, hexane, heptane, benzene, toluene, xylene.

5. The preparation method according to claim 2, wherein The terminator is one of water, ethanol, propanol, butanol, and the mass ratio of the terminator to the trans rubber alloy is 0.1 - 4:100; the chelating agent is one or several of ethylenediaminetetraacetate, ethylenediaminetriaminepentaacetate, sodium nitrilotriacetate, oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, citrates, tartrates, gluconates, benzotriazole, guanidine derivatives, hydroxyethylidene-1,1-diphosphonate, aminotrimethylenephosphonate, diethylenetriaminepenta(methylene phosphonic acid), triethylenetetraminehexa(methylene), bis(1,6-hexylene)triaminepenta(methylene phosphonic acid), polyamino polyether tetra(methylene phosphonic acid), polyvinyl alcohol, polyethylene glycol, polymethacryloylacetone, polyacryloylacetone, vinyl acetate - allyl acetoacetate copolymer, polyaniline, polydopamine, styrene - maleic anhydride copolymer, polyurethane elastomer, polyether elastomer, etc., and the mass ratio of the chelating agent to the trans rubber alloy is 0.1 - 4:

100.

6. The preparation method according to claim 2, wherein, The antioxidant is one or two of phenolic antioxidants, amine antioxidants, phosphite antioxidants, thioester antioxidants, and the mass ratio of the antioxidant to the trans rubber alloy is 0.1 - 4:100; the filler is one or two of various types of carbon black and white carbon black, and the mass ratio of the filler to the trans rubber alloy is 0 - 100:

100.

7. The trans rubber alloy material according to claim 1, characterized in that, The mass ratio of zinc oxide to the trans rubber alloy is 0 - 6:100; the mass ratio of magnesium oxide to the trans rubber alloy is 0 - 6:100; the mass ratio of the coupling agent to the trans rubber alloy is 0 - 10:

100.

8. The trans rubber alloy material according to claim 1, characterized in that, The trans rubber alloy material has good heat aging resistance.

9. The trans rubber alloy material according to claim 1, characterized in that, In the trans rubber alloy material described above, the butadiene-isoprene random copolymer with a trans-1,4 structure provides excellent comprehensive properties; the butadiene-isoprene copolymer containing a longer trans-1,4-polybutadiene block provides a high-melting-point trans-1,4-polybutadiene nanosheet crystal structure, and the butadiene-isoprene copolymer containing a longer trans-1,4-polyisoprene block provides a low-melting-point nanosheet crystal structure. The copolymer of the two block-structured polymers contributes high strength, high modulus, and excellent dynamic fatigue performance to the trans rubber alloy. When applied to the tread rubber and sidewall rubber of truck tires, car tires, and giant tires, as well as rubber damping products, it can significantly improve the high-temperature dynamic fatigue life of the products.

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