A semi-hydrogenated bio-based terpene and conjugated diene multivariate random copolymer elastomer, and a preparation method and application thereof

Abstract

A semi-hydrogenated bio-based terpene and conjugated diene multivariate random copolymer elastomer and its preparation method and application. The present application belongs to the field of olefin catalytic polymerization and hydrogenation. The purpose of the present application is to solve the technical problem that the existing hydrogenated rubber material generally does not have good skid resistance and mechanical properties. The elastomer of the present application is copolymerized and hydrogenated by at least one of the conjugated diene monomers and at least one of the bio-based terpene monomers, and the hydrogenation degree is 40-55%. The present application copolymerizes bio-based terpene and conjugated diene monomers, then hydrogenates them, controls the hydrogenation process, and finally obtains a bio-based semi-hydrogenated elastomer with only half the hydrogenation degree. Because this elastomer has a longer side chain and only half the hydrogenation degree, it has all the properties of elastomers and plastics. This elastomer has excellent mechanical properties, weather resistance and skid resistance, the overall preparation process is simple and the yield is high, and it is extremely suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of olefin catalytic polymerization and hydrogenation, specifically relating to a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, its preparation method, and its application. Background Technology

[0002] Rapid industrialization and motorization have led to increased demand for fossil fuels such as oil, while the consumption of fossil fuels has resulted in greater greenhouse gas emissions. Traditional fossil fuels are proving insufficient to meet the growing demands of national defense and civilian life, prompting countries worldwide to urgently seek more efficient, lower-cost, and sustainable alternative resources. Biomass energy is currently considered a viable alternative to fossil fuels to some extent. It primarily utilizes plant photosynthesis to convert solar energy, carbon dioxide, and water into corresponding bio-based compounds. These bio-based compounds release water and carbon dioxide during use, creating a theoretically zero-emission and recyclable process. Therefore, bio-based compounds are considered the only form of solar energy that can be stored and are also an economically feasible and effective solution to global environmental pollution problems. This type of bio-based energy possesses enormous potential to replace fossil fuels to a certain extent.

[0003] Countries worldwide are actively implementing policies to utilize biomass resources for the extraction and production of bio-based fuels and chemicals. Bio-based polymers are already finding applications in production and daily life, such as in medical and packaging materials. Special hydrogenation treatment of bio-based polymers, such as terpenes like myrcene and farnesene, can yield a relatively saturated elastomer. Because the polymer chain structure has a certain degree of saturation, the hydrogenated rubber material exhibits good oil resistance (good resistance to fuel oil, lubricating oil, and aromatic solvents). Furthermore, this saturated structure also gives the rubber material excellent heat resistance, chemical corrosion resistance (good resistance to acids, alkalis, and Freon), ozone resistance, and compression set resistance. Simultaneously, because bio-based terpenes such as β-myrcene and β-farnesene have long side chains, they possess better anti-slip properties. However, current research on hydrogenated rubber materials is limited to fossil fuel-based polymers, with almost no research on bio-based polymers. Therefore, exploring the hydrogenation of bio-based polymers is of great scientific and industrial value. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing hydrogenation research systems, and to provide a semi-hydrogenated elastomer with high anti-slip properties and excellent mechanical properties. Ultimately, this invention proposes a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, its preparation method, and its applications.

[0005] The technical solution of the present invention is as follows:

[0006] One objective of this invention is to provide a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, wherein the elastomer is copolymerized and hydrogenated from at least one conjugated diene monomer and at least one bio-based terpene monomer, with a degree of hydrogenation of 30-60%, a number-average molecular weight of 1.0-500,000 g / mol, a molecular weight distribution of 1.0-5.0, a molar content of 5-95% of the conjugated diene polymer unit, and a molar mass of 5-95% of the bio-based terpene polymer unit.

[0007] Preferably, the conjugated diene monomers include 1,3-butadiene, isoprene, 1,5-hexadiene, and 1,7-octadiene, and the bio-based terpene monomers are monoterpenes and / or sesquiterpenes.

[0008] More preferably, the conjugated diene monomer is 1,3-butadiene or isoprene.

[0009] More preferably, the monoterpenes are geraniol, limonene, α-myrcene, β-myrcene, β-citronellol, citral, or menthol, and the sesquiterpenes are juniperene, α-farnesene, β-farnesene, cedrene, or caryophyllene.

[0010] Most preferably, the monoterpene is β-myrcene and the sesquiterpene is β-farnesene.

[0011] Preferably, the degree of hydrogenation is 45-52%, the molecular weight distribution is 1.9-3.2, the molar content of conjugated diene polymer units is 10-90%, and the molar mass of bio-based terpene polymer units is 10-90%.

[0012] Preferably, the glass transition temperature range is -80 to 0℃, the tanδ value at 0℃ is 0.7 to 1.3, the tear strength is >28 N / mm, the elongation at break is >520%, the Shore hardness A is >40, the heat distortion temperature is >80℃, and the embrittlement temperature is <-35℃.

[0013] More preferably, the glass transition temperature range is -55 to -19℃, the tanδ value at 0℃ is 0.96 to 1.21, the tear strength is >32 N / mm, the elongation at break is >560%, the Shore hardness A is >51, the heat distortion temperature is >96℃, and the embrittlement temperature is <-43℃.

[0014] The second objective of this invention is to provide a method for preparing a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, the method comprising the following steps:

[0015] (1) A multi-component random copolymer was prepared by copolymerizing conjugated diene monomers and bio-based terpene monomers;

[0016] (2) The copolymer solution was prepared by dissolving the multi-component random copolymer in a solvent. The copolymer solution, catalyst and co-catalyst were added to the dry high-temperature reactor in sequence under an argon atmosphere. The gas in the reactor was replaced three times with hydrogen. The reactor was reacted for 1 to 3 hours at a speed of 100 to 1000 rpm, a hydrogenation reaction pressure of 1 to 3 MPa and a temperature of 10℃ to 40℃ to obtain a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer.

[0017] Alternatively, a metallocene hydrogenation reaction system can be used. Under an argon atmosphere, a copolymer solution and a bis(titanium)-based / alkylaluminum / lithium-based metal compound composite catalyst are sequentially added to a dry, high-temperature reactor. The gas in the reactor is replaced three times with hydrogen. The reactor rotation speed is adjusted to 100–1500 rpm, the hydrogenation reaction pressure is 0.1–1.5 MPa, the temperature is increased to 10°C–60°C, and the reaction is carried out for 1–2 hours to obtain a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer.

[0018] Preferably, the copolymerization in step (1) is carried out by anionic polymerization, cationic polymerization, free radical polymerization or coordination polymerization.

[0019] Preferably, the specific process of anionic polymerization is as follows:

[0020] Copolymerization is initiated under anhydrous and oxygen-free conditions, with an organoalkali metal as the initiator and / or an organoaluminum compound as the cocatalyst. More preferably, the organoalkali metal is one or more of n-butyllithium, sec-butyllithium, tert-butyllithium, tert-butoxide lithium, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, phenyllithium, benzyllithium, and naphthol. The organoaluminum compound is abbreviated as AB, where A represents one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, dichloroethylaluminum, dichloroethylaluminum, or sesquiethylaluminum chloride, and B represents one or more of 2,6-di-tert-butyl-p-cresol, epi-2,6-di-tert-butylphenol, 2-tert-butylphenol, or 2,6-di-tert-butyl-4-ethylphenol. The reaction temperature is -50°C to 70°C, and the reaction time is 10 min to 360 min. More preferably, the reaction temperature is 30°C to 50°C, and the reaction time is 30 min to 120 min.

[0021] Preferably, the coordination polymerization method includes iron coordination polymerization, Ziegnera-type catalytic system polymerization, cationic lutetium coordination complex polymerization with β-diaminosulfonate as ligand, rare earth lanthanide catalytic polymerization system polymerization, [OSSO] type titanium complex polymerization, semi-sandwich scandium complex polymerization, and cobalt catalytic system polymerization.

[0022] More preferably, the specific process of using the iron coordination polymerization method is as follows:

[0023] Under anhydrous and oxygen-free conditions, an iron catalyst, a co-catalyst, a conjugated diene monomer, a bio-based terpene monomer, and a solvent are added to a reactor, and the polymerization reaction is carried out with stirring at -30 to 100°C for 10 to 120 minutes. More preferably, the reaction temperature is -20°C to 30°C, and the reaction time is 30 minutes. The iron catalyst is any one of the following structural formulas:

[0024]

[0025] Preferably, the concentration of the copolymer solution in step (2) is 10 wt%, and the solvent of the copolymer solution is one or more of toluene, xylene, n-hexane, and cyclohexane.

[0026] Preferably, the catalyst in the Ziegler-Natta hydrogenation reaction system is one or more of palladium dichloride, platinum dichloride, platinum tetrachloride, vanadium trichloride, cobalt chloride, titanium tetrachloride, nickel chloride, and nickel naphthenate. More preferably, the catalyst is nickel naphthenate.

[0027] Preferably, the cocatalyst is an organometallic compound of a metal from Group IA to Group IIIA. More preferably, the cocatalyst is one or more of aluminum chloride, diethylaluminum chloride, tri-n-hexylaluminum, aluminum tert-butoxide, aluminum nitrate, dimethylaluminum chloride, diisobutylaluminum hydride, and methylaluminoxane.

[0028] Preferably, the mass ratio of copolymer to catalyst in the copolymer solution is (1-500):1, and the molar ratio of catalyst to co-catalyst is 1:(1-9).

[0029] Preferably, the bis-titanium hydride reaction system comprises dichlorotitanium hydride, and the alkyl aluminum is one or more selected from trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, dichlorodiethylaluminum, dichloroethylaluminum, and diisobutylaluminum hydride; more preferably, the alkyl aluminum is triisobutylaluminum. The lithium-based metal compound is one or more selected from lithium hydride, lithium isopropoxide, ethyl lithium, isopropyl lithium, lithium carbonate, lithium amide, lithium sulfate, and lithium aluminum hydroxide; more preferably, the lithium-based metal compound is lithium hydride.

[0030] Preferably, the mass ratio of the copolymer to the diacetic titanium in the copolymer solution is (1-6000):1, the molar ratio of the diacetic titanium to the alkyl aluminum compound is 1:(1-9), and the molar ratio of the diacetic titanium to the lithium metal compound is 1:(1-10).

[0031] The third objective of this invention is to provide an elastomer that combines high mechanical properties, anti-slip properties, and resistance to deformation, which is formed by vulcanization of the above-mentioned semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer.

[0032] Preferably, the elastomer possessing high mechanical properties, anti-slip properties, and resistance to deformation has a Shore hardness A > 40, a resilience modulus > 20%, an elongation at break > 300%, and a tear strength > 20 N / mm.

[0033] The fourth objective of this invention is to provide a method for preparing an elastomer that combines high mechanical properties, anti-slip properties, and resistance to deformation, wherein the method includes:

[0034] Weigh out 100 parts by weight of semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, 5-70 parts of carbon black, 1-4 parts of vulcanization accelerator, 0.1-10 parts of sulfur, 1-8 parts of zinc oxide, 1-10 parts of zinc stearate, 0.5-5 parts of antioxidant and 1-20 parts of filler oil, mix them, and then knead and vulcanize them.

[0035] Preferably, the carbon black is one or more of N324, N110, and N320; the vulcanization accelerator is one or more of NS, NA-22, NOBS, CZ, and DCBS; the antioxidant is one or more of quinoline, p-phenylenediamine, or naphthylamine; and the filler oil is one or more of paraffin oil, naphthenic oil, or aromatic oil.

[0036] The fifth objective of this invention is to provide an elastomer that combines high mechanical properties, anti-slip properties, and resistance to deformation for use in industrial materials, building materials, and consumer goods.

[0037] The advantages of this invention compared to existing technologies are:

[0038] This invention first copolymerizes a bio-based terpene monomer with a conjugated diene monomer to obtain a multi-component random copolymer, then hydrogenates it to obtain a bio-based semi-hydrogenated elastomer with only half the degree of hydrogenation. This elastomer, due to its longer side chains and lower hydrogenation, possesses all the properties of both elastomers and plastics, exhibiting excellent mechanical properties, anti-slip properties, and resistance to deformation. The overall preparation process is simple and has a high yield, making it highly suitable for industrial production. Currently, research on bio-based hydrogenated elastomers is largely nonexistent; therefore, this invention possesses high inventiveness and effectively promotes the development of polymer materials in my country. Attached Figure Description

[0039] Figure 1 The binary copolymer obtained in Example 1 1 H NMR spectrum;

[0040] Figure 2 The hydrogenated binary copolymer obtained in Example 1 1 H NMR spectrum;

[0041] Figure 3 The GPC spectrum of the hydrogenated binary copolymer obtained in Example 1 is shown below.

[0042] Figure 4 The image shows the DSC spectrum of the hydrogenated binary copolymer obtained in Example 1. Detailed Implementation

[0043] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in this invention, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0044] When equivalents, concentrations, or other values ​​or parameters in the invention are expressed as ranges, preferred ranges, or a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. In this specification and claims, range definitions may be combined and / or interchanged, unless otherwise stated, these ranges include all sub-ranges contained therein.

[0045] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0046] In this invention, "an embodiment" or "embodiment" refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that excludes other embodiments.

[0047] The endpoints and any values ​​of the ranges disclosed in this invention 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0048] This invention provides a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, wherein the elastomer is copolymerized and hydrogenated from at least one conjugated diene monomer and at least one bio-based terpene monomer, with a degree of hydrogenation of 30-60%, a number-average molecular weight of 1.0-500,000 g / mol, a molecular weight distribution of 1.0-5.0, a molar content of 5-95% of the conjugated diene polymer unit, and a molar mass of 5-95% of the bio-based terpene polymer unit.

[0049] In optional embodiments, the conjugated diene monomer includes 1,3-butadiene, isoprene, 1,5-hexadiene, and 1,7-octadiene. More preferably, the conjugated diene monomer is 1,3-butadiene or isoprene.

[0050] In optional embodiments, the bio-based terpene monomers are monoterpenes and / or sesquiterpenes. More preferably, the monoterpenes are geraniol, limonene, α-myrcene, β-myrcene, β-citronellol, citral, or menthol, and the sesquiterpenes are juniperene, α-farnesene, β-farnesene, cedrene, or caryophyllene. Most preferably, the monoterpenes are β-myrcene, and the sesquiterpenes are β-farnesene.

[0051] In an optional embodiment, the degree of hydrogenation is 45-52%, the molecular weight distribution is 1.9-3.2, the molar content of conjugated diene polymer units is 10-90%, and the molar mass of bio-based terpene polymer units is 10-90%.

[0052] In an optional embodiment, the glass transition temperature range is -80 to 0°C, the tanδ value at 0°C is 0.7 to 1.3, the tear strength is >28 N / mm, the elongation at break is >520%, the Shore hardness A is >40, the heat distortion temperature is >80°C, and the embrittlement temperature is <-35°C.

[0053] In an optional embodiment, the glass transition temperature range is -55 to -19°C, the tanδ value at 0°C is 0.96 to 1.21, the tear strength is >32 N / mm, the elongation at break is >560%, the Shore hardness A is >51, the heat distortion temperature is >96°C, and the embrittlement temperature is <-43°C.

[0054] This invention also provides a method for preparing a multi-component random copolymer elastomer of semi-hydrogenated bio-based terpenes and conjugated dienes, the method comprising the following steps:

[0055] (1) A multi-component random copolymer was prepared by copolymerizing conjugated diene monomers and bio-based terpene monomers;

[0056] (2) The multi-component random copolymer is dissolved in a solvent to obtain a copolymer solution, and then hydrogenated using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer.

[0057] In optional embodiments, the preparation of the multi-component random copolymer in step (1) is carried out by anionic polymerization, cationic polymerization, free radical polymerization, or coordination polymerization. More preferably, coordination polymerization, anionic polymerization, or free radical polymerization is used. More preferably, coordination polymerization or anionic polymerization is used.

[0058] In optional embodiments, the coordination polymerization method includes iron coordination polymerization, Ziegnerata-type catalytic system polymerization, cationic lutetium coordination complex polymerization with β-diaminosulfonate as ligand, rare earth lanthanide catalytic polymerization, [OSSO]-type titanium complex polymerization, semi-sandwich scandium complex polymerization, and cobalt catalytic system polymerization. More preferably, it includes iron coordination polymerization, cationic lutetium coordination complex polymerization with β-diaminosulfonate as ligand, rare earth lanthanide catalytic polymerization, [OSSO]-type titanium complex polymerization, and cobalt catalytic system polymerization. More preferably, it includes iron coordination polymerization, cationic lutetium coordination complex polymerization with β-diaminosulfonate as ligand, and rare earth lanthanide catalytic polymerization. Most preferably, it includes iron coordination polymerization.

[0059] In an optional embodiment, when the preparation of the multi-component random copolymer is carried out by iron coordination polymerization, the specific steps are as follows: under anhydrous and oxygen-free conditions, an iron catalyst, a co-catalyst, a conjugated diene monomer, a bio-based terpene monomer, and a solvent are added to the reactor, and the polymerization reaction is stirred at -30℃ to 100℃ for 10 min to 120 min. After the reaction is completed, a quencher and an anti-aging agent are added, and after washing, the mixture is vacuum dried to constant weight to obtain a multi-component random copolymer of conjugated diene and bio-based terpene.

[0060] In an optional embodiment, the reaction temperature is -20°C to 30°C, more preferably 0°C to 30°C; the reaction time is 30 min.

[0061] In an optional embodiment, when using iron coordination polymerization, the iron catalyst is any one of the following structural formulas:

[0062]

[0063] In optional embodiments, the solvent is one or more of cyclohexane, n-hexane, petroleum ether, toluene, and xylene, and the ratio of the solvent to the total volume of the comonomer is (1-50):1, more preferably (7-20):1; the molar ratio of the total molar amount of the comonomer to the molar amount of iron in the iron catalyst is (100-50000):1, more preferably (150-5000):1.

[0064] In optional embodiments, the co-catalyst is a single component or a two-component catalyst. When the co-catalyst is a single component, it is selected from one or more of methylaluminoxane (MAO), dried methylaluminoxane (DMAO), and modified methylaluminoxane (MMAO). The molar ratio of aluminum in the co-catalyst to iron in the iron catalyst is (100-1500):1, more preferably 500:1. When the co-catalyst is a two-component catalyst, component A is selected from one or more of trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, diethylaluminum chloride, dichloroethylaluminum, diisobutylaluminum hydride, and sesquiethylaluminum chloride. The formulation includes multiple components, with component B being one or more of the following: methylaluminoxane (MAO), dried methylaluminoxane (DMAO), modified methylaluminoxane (MMAO), N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, 4-isopropyl-4'-methyldiphenyliodide tetra(pentafluorophenyl)borate, triphenylphosphine oxide, tri(pentafluorophenyl)phosphine, and triphenylphosphine. The molar ratio of aluminum in component A to iron in the iron catalyst is (1-100):1, more preferably 40:1. The molar ratio of aluminum, boron, or phosphine in component B to iron in the iron catalyst is (1-20):1, more preferably 1:1.

[0065] In an optional embodiment, when the preparation of the multi-component random copolymer is carried out by anionic polymerization, the specific steps are as follows: under anhydrous and oxygen-free conditions, an organic alkali metal is used as an initiator to initiate the copolymerization of conjugated diene monomers and bio-based terpene monomers. After reacting at a certain temperature for a certain time, ethanol is added to quench the reaction and obtain the polymer product.

[0066] Alternatively, under anhydrous and oxygen-free conditions, an organoalkali metal is used as an initiator and an organoaluminum compound is used as a cocatalyst to initiate the copolymerization of conjugated diene monomers and bio-based terpene monomers. After reacting at a certain temperature for a certain time, ethanol is added to quench the reaction and obtain the polymer product.

[0067] In optional embodiments, the organic alkali metal is one or more of n-butyllithium, sec-butyllithium, tert-butyllithium, tert-butoxide lithium, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, phenyllithium, benzyllithium, and naphthyllithium; more preferably, it is one or more of n-butyllithium, sec-butyllithium, tert-butyllithium, and n-propyllithium.

[0068] In an optional embodiment, the reaction temperature is -50℃ to 70℃ and the reaction time is 10 min to 360 min; more preferably, the reaction temperature is 30℃ to 50℃ and the reaction time is 30 min to 120 min.

[0069] In optional embodiments, the solvent is one or more selected from THF, toluene, ethylbenzene, xylene, n-hexane, cyclohexane, dichloromethane, chloroform, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and methyl tert-butyl ether; more preferably, it is one or more selected from THF, toluene, ethylbenzene, n-hexane, cyclohexane, ethylene glycol dimethyl ether, and methyl tert-butyl ether.

[0070] In an optional embodiment, the organoaluminum compound may be abbreviated as AB, where A represents one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, or sesquiethylaluminum chloride, and B represents one or more of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2-tert-butylphenol, or 2,6-di-tert-butyl-4-ethylphenol, and the molar ratio of A to B is (0.1–2):1.

[0071] In optional embodiments, the total volume ratio of solvent to comonomer is (1-50):1, more preferably 3:1; the total molar amount of comonomer to the molar ratio of lithium in the initiator is (100-50000):1, more preferably 1556:1; and the total molar amount of comonomer to the molar ratio of aluminum in the cocatalyst is (13-6250):1, more preferably 195:1.

[0072] In optional embodiments, when the preparation of the multi-component random copolymer is carried out by free radical polymerization, examples include: hydrogen peroxide polymerization, emulsion polymerization, nitrile radical polymerization (NMP), and reversible addition chain transfer polymerization (RAFT). Among these methods, nitrile radical polymerization (NMP) and reversible addition chain transfer polymerization are preferred; the most preferred method is reversible addition chain transfer polymerization, and the initiator is one or more of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptanenitrile, azodihydroxyvalerate, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyramidin hydrochloride, and azoisobutyrocyanoformamide.

[0073] In optional embodiments, when the preparation of the multi-component random copolymer is carried out by cationic polymerization, examples include: cationic polymerization of β-myrcene using a dispersible Lewis acid surfactant combination catalyst (LASC) prepared from ytterbium chloride and sodium alkylbenzene sulfonate surfactants; trifluoromethanesulfonate initiation system; boron trifluoride diethyl ether initiation system; etc., with LASC polymerization being the preferred method among these.

[0074] In an optional embodiment, the polymerization reaction can be quenched by adding a protic compound such as methanol, a methanol solution of acetic acid, or a methanol solution of hydrochloric acid to the reaction solution; or an aqueous solution of acetic acid or hydrochloric acid.

[0075] In an optional embodiment, the concentration of the copolymer solution in step (2) is 10 wt%.

[0076] In an optional embodiment, the solvent of the copolymer solution in step (2) is one or more of toluene, xylene, n-hexane, and cyclohexane.

[0077] In an optional implementation, the specific hydrogenation process in step (2) using the Ziegler-Natta hydrogenation reaction system is as follows:

[0078] Under an argon atmosphere, the copolymer solution, catalyst, and co-catalyst were sequentially added to a dry, high-temperature reactor. The reactor was purged three times with hydrogen. The reactor rotation speed was adjusted to 100–1000 rpm, the hydrogenation reaction pressure was 1–3 MPa, and the temperature was increased to 10–40 °C for 1–3 h. After the reaction, the system was cooled to room temperature, and anhydrous ethanol was added. The hydrogenated elastomer was separated as a precipitate. The precipitate was dried at room temperature in a vacuum oven to constant weight, yielding the final semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer.

[0079] In optional embodiments, the catalyst is one or more of palladium dichloride, platinum dichloride, platinum tetrachloride, vanadium trichloride, cobalt chloride, titanium tetrachloride, nickel chloride, and nickel naphthenate, with nickel naphthenate being the most preferred; the co-catalyst is an organometallic compound of a metal from Group IA to Group IIIA, more preferably one or more of aluminum chloride, diethylaluminum chloride, tri-n-hexylaluminum, aluminum tert-butoxide, aluminum nitrate, dimethylaluminum chloride, diisobutylaluminum hydride, and methylaluminoxane, with methylaluminoxane being the most preferred.

[0080] In an optional embodiment, the mass ratio of copolymer to catalyst in the copolymer solution is (1-500):1, more preferably 350:1; the molar ratio of catalyst to co-catalyst is 1:(1-9), more preferably 1:6; the hydrogenation reaction temperature is preferably 25°C; the hydrogenation reaction pressure is preferably 3 MPa; the rotation speed of the hydrogenation reactor is preferably 500 rpm; and the hydrogenation reaction time is preferably 1.5 h.

[0081] In optional embodiments, the metallocene hydrogenation reaction system in step (2) includes a bis-titanium / lithium hydride / aromatic ester system, a bis-titanium or mono-titanium / triphenyl lithium system, a bis-titanium / alkylaluminum / silica ester system, or a bis-titanium / alkylaluminum / lithium metal compound system.

[0082] In an optional implementation, the specific process of hydrogenation using a dicaprocinoxane / alkylaluminum / lithium-based metal compound system is as follows:

[0083] Under an argon atmosphere, a copolymer solution and a bis(titanium)-based / alkylaluminum / lithium-based metal compound composite catalyst were sequentially added to a dry, high-temperature reactor. The reactor was purged three times with hydrogen. The reactor rotation speed was adjusted to 100–1500 rpm, the hydrogenation reaction pressure was 0.1–1.5 MPa, and the temperature was increased to 10–60 °C for 1–2 hours. After the reaction, the system was cooled to room temperature, and anhydrous ethanol was added. The hydrogenated elastomer was separated as a precipitate. The precipitate was dried at room temperature to constant weight in a vacuum oven to obtain the final semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer.

[0084] In an optional embodiment, the catalyst, bis(titanium)-dichlorotitanium, comprises bis(titanium)-dichlorotitanium; the co-catalyst, alkylaluminum, is one or more of trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum hydride, more preferably triisobutylaluminum; and the lithium metal compound is one or more of lithium hydride, lithium isopropoxide, ethyl lithium, isopropyl lithium, lithium carbonate, lithium amino, lithium sulfate, and lithium aluminum hydroxide, more preferably lithium hydride.

[0085] In an optional embodiment, the mass ratio of the copolymer to the diacetic titanium in the copolymer solution is (1-6000):1, more preferably 4500:1; the molar ratio of the diacetic titanium to the alkyl aluminum compound is 1:(1-9), more preferably 1:5; the molar ratio of the diacetic titanium to the lithium metal compound is 1:(1-10), more preferably 1:6; the hydrogenation reaction temperature is preferably 40°C; the hydrogenation reaction pressure is preferably 1 MPa; the rotation speed of the hydrogenation reactor is preferably 650 rpm; and the hydrogenation reaction time is preferably 1 h.

[0086] This invention first copolymerizes a bio-based terpene monomer with a conjugated diene monomer to obtain a multi-component random copolymer, then hydrogenates it to obtain a bio-based semi-hydrogenated elastomer with only half the degree of hydrogenation. This elastomer, due to its longer side chains and lower hydrogenation, possesses all the properties of both elastomers and plastics, exhibiting excellent mechanical properties, anti-slip properties, and resistance to deformation. The overall preparation process is simple and has a high yield, making it highly suitable for industrial production. Currently, research on bio-based hydrogenated elastomers is largely nonexistent; therefore, this invention possesses high inventiveness and effectively promotes the development of polymer materials in my country.

[0087] The present invention also provides an elastomer with high mechanical properties, anti-slip properties, and resistance to deformation. The elastomer with high mechanical properties, anti-slip properties, and resistance to deformation is formed by vulcanization of the aforementioned semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer.

[0088] In an optional embodiment, the vulcanized elastomer has a Shore hardness A > 40, a resilience modulus > 20%, an elongation at break > 300%, and a tear strength > 20 N / mm.

[0089] This invention also provides a method for preparing an elastomer that combines high mechanical properties, anti-slip properties, and resistance to deformation, wherein the method includes:

[0090] Weigh out 100 parts by weight of semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, 5-70 parts of carbon black, 1-4 parts of vulcanization accelerator, 0.1-10 parts of sulfur, 1-8 parts of zinc oxide, 1-10 parts of zinc stearate, 0.5-5 parts of antioxidant and 1-20 parts of filler oil, mix them, and then knead and vulcanize them.

[0091] In an optional embodiment, the carbon black is one or more of N324, N110, and N320.

[0092] In an optional embodiment, the vulcanization accelerator is one or more of NS, NA-22, NOBS, CZ, and DCBS.

[0093] In an optional embodiment, the antioxidant is one or more of quinoline, p-phenylenediamine, or naphthylamine.

[0094] In an optional embodiment, the filler oil is one or more of paraffin oil, naphthenic oil, or aromatic oil.

[0095] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0096] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0097] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0098] When the equivalent, concentration, or other value or parameter described in the following embodiments is expressed as a range, preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. In this specification and claims, range definitions may be combined and / or interchanged, unless otherwise stated, these ranges include all sub-ranges contained therein.

[0099] In the following embodiments, the indefinite articles “a” and “an” preceding an element or component do not impose any limitation on the quantity requirement (i.e., the number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0100] In the following embodiments, "an embodiment" or "embodiment" refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that excludes other embodiments.

[0101] The endpoints and any values ​​of the ranges disclosed in the following embodiments 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0102] The mechanical performance testing standard in the following embodiments is GB / T 589-2009;

[0103] The standard for heat deformation temperature testing is: refer to GB / T1634-2019;

[0104] The standard for embrittlement temperature testing is: refer to GB / T 5470-2008.

[0105] Example 1: The preparation method of an elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example is as follows:

[0106] (1) Polymerization: Under an argon atmosphere, anhydrous toluene (120 mL), β-myrcene (0.26 mL, 1.6 mmol, 156 equiv.), isoprene (1.4 mL, 14 mmol, 1400 equiv.), MAO reagent (5.0 mmol, 500 equiv.), and catalyst 5 (1.0 mL, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 30 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0107] (2) Hydrogenation: A 10 wt% hexane mother liquor of the copolymer was prepared in a 500 mL Schlenk tube. The catalyst, nickel naphthenate (14.3 mg, 35.6 μmol, 1 equiv.), and the co-catalyst, methylaluminoxane (18 mL, 1.8 mmol, 6 equiv.), were added sequentially to the Schlenk tube under an argon atmosphere, and the mixture was stirred for 20 mins. The reactor was dried, and 200.0 mL of the 10 wt% hexane mother liquor of the copolymer and the catalyst and co-catalyst reaction mixture were added under an argon atmosphere. The reactor was purged three times with H2, and the pressure inside was 3 MPa after purging. Stirring was started, the hydrogenation temperature was 25℃, the hydrogenation time was 1.5 h, and the rotation speed was 500 rpm. After the reaction, the hydrogenation reactor was cooled to room temperature, depressurized, and allowed to stand for 30 mins before being opened. Anhydrous ethanol was added and stirred to obtain the hydrogenated white elastomer. The performance test results are shown in Table 1.

[0108] (3) Mixing and vulcanization: 100 parts by mass of the hydrogenated white elastomer obtained in step (2), 45 parts of N220, 2.5 parts of vulcanizing agent CZ, 2.5 parts of sulfur, 2.5 parts of zinc oxide, 1.5 parts of zinc stearate, 2 parts of ethoxyquinoline antioxidant (Bermuda Biotechnology Co., Ltd.), and 15 parts of aromatic oil were vulcanized. After mixing and vulcanization, a reinforced semi-hydrogenated β-myrcene-isoprene binary random copolymer composite material was obtained. The mechanical property test results are shown in Table 2.

[0109] Example 2: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that: in step (1), the bio-based terpene monomer is replaced with β-farnesene, the amount of β-farnesene added is (0.04 mL, 0.16 mmol, 15.6 equiv.), the amount of isoprene added is (0.14 mL, 1.4 mmol, 140 equiv.), and the amount of anhydrous toluene added as the reaction solvent is (1.8 mL). Other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0110] Example 3: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that the conjugated diene monomer in step (1) is replaced with 1,3-butadiene, and the amount of 1,3-butadiene added is (1.16 mL, 14 mmol, 1400 equiv.). Other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0111] Example 4: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that the monomer molar ratio in step (1) is changed: β-myrcene:isoprene = 1:1; β-myrcene (4.2 mL, 25.0 mmol, 2500 equiv.) and isoprene (2.5 mL, 25.0 mmol, 2500 equiv.), and the amount of anhydrous toluene added as the reaction solvent is (65 mL). Other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0112] Example 5: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that the monomer molar ratio in step (1) is changed, β-myrcene:isoprene = 9:1; β-myrcene (2.4 mL, 14.0 mmol, 1400 equiv.) and isoprene (0.17 mL, 1.56 mmol, 156 equiv.), and the amount of anhydrous toluene added as the reaction solvent is (25.7 mL). Other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0113] Example 6: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that: in step (1), anhydrous toluene (70 mL), isoprene (3.5 mL, 35.0 mmol, 3500 equiv.), β-myrcene (1.3 mL, 7.5 mmol, 750 equiv.), and β-farnesene (2.1 mL, 7.5 mmol, 750 equiv.) are used, while other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0114] Example 7: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that: in step (1), anhydrous toluene (70 mL), 1,3-butadiene (2.9 mL, 35.0 mmol, 3500 equiv.), β-myrcene (1.3 mL, 7.5 mmol, 750 equiv.), and β-farnesene (2.1 mL, 7.5 mmol, 750 equiv.) are used, while other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0115] Example 8: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that: in step (1), anhydrous toluene (124 mL), isoprene (1.75 mL, 17.5 mmol, 1750 equiv.), 1,3-butadiene (1.45 mL, 17.5 mmol, 1750 equiv.), β-myrcene (1.25 mL, 7.5 mmol, 750 equiv.), and β-farnesene (2.05 mL, 7.5 mmol, 750 equiv.) are used, while other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0116] Example 9: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and non-deformation resistance in this example differs from that in Example 1 in that the amount of anhydrous toluene added in step (1) is 36 mL, while the other steps and parameters are the same as in Example 1. The performance test results of the hydrogenated product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0117] Example 10: The preparation method of the elastomer with high mechanical properties, anti-slip properties, and resistance to deformation in this example differs from that in Example 1 in that: in step (1), the iron catalyst is replaced with No. 1, the amount added is (1.0 ml, 10 μmol, 1 equiv.), and the reaction temperature is -20℃; other steps and parameters are the same as in Example 1. The performance test results of the hydrogenation product before sulfidation are shown in Table 1. The mechanical property test results of the product after sulfidation are shown in Table 2.

[0118] Example 11: The preparation method of the elastomer with high mechanical properties, anti-slip properties and non-deformation properties in this example is different from that in Example 1: anionic polymerization is used in step (1), while other steps and parameters are the same as in Example 1.

[0119] (1) Polymerization: Under an argon atmosphere, anhydrous toluene (5 mL) and i-BuAl(BHT) were added sequentially to a 50 mL reaction flask. 1.9 Aluminum reagent (5 mL, 1.6 mmol, 8 equiv.), initiator sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.), β-myrcene (0.26 mL, 1.6 mmol, 156 equiv.), and isoprene (1.4 mL, 14 mmol, 1400 equiv.) were polymerized at 25 °C for 30 min. The reaction was then terminated with a mixture of 5 mL methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol and dried under vacuum at 40 °C to constant weight to obtain the elastomer polymer. The performance test results of the hydrogenated product before vulcanization are shown in Table 1. The mechanical property test results of the product after vulcanization are shown in Table 2.

[0120] Example 12: The preparation method of the elastomer with high mechanical properties, anti-slip properties and non-deformation properties in this example is different from that in Example 1: the hydrogenation reaction system in step (2) is replaced with a bis(titanium)-alkylaluminum-lithium metal compound hydrogenation system, and the other steps and parameters are the same as in Example 1.

[0121] (2) The hydrogenation process was as follows: A 10 wt% xylene mother liquor of the copolymer was prepared in a 500 mL Schlenk tube. The reactor was dried and heated to 40°C. Under an argon atmosphere, 200.0 mL of the 10 wt% xylene mother liquor of the copolymer, along with catalysts diazocarpine (4.4 mg, 17.7 μmol, 1 equiv.), triisobutylaluminum (0.08 mL, 88.5 μmol, 5 equiv.), and lithium hydride (0.84 mg, 106.2 μmol, 6 equiv.), were added sequentially. The mixture was stirred at 600 rpm for 20 min. The reactor was purged three times with H2, and after pressurization, the pressure inside the reactor was 1 MPa. Stirring was then initiated, and the hydrogenation temperature was 40°C. The hydrogenation time was 1 h, and the stirring speed was 650 rpm. After the reaction, the hydrogenation reactor was cooled to room temperature, depressurized, and allowed to stand for 30.0 min before being opened. Anhydrous ethanol was added and stirred to obtain the hydrogenated white elastomer. Other steps and parameters were the same as in Example 1. The performance test results of the hydrogenation products before sulfidation are shown in Table 1. The mechanical performance test results of the products after sulfidation are shown in Table 2.

[0122] Table 1. Physical property test data of semi-hydrogenated bio-based terpenes and conjugated dienes multi-component random copolymer elastomers before vulcanization.

[0123]

[0124]

[0125] Table 2. Mechanical property test data of semi-hydrogenated bio-based terpenes and conjugated dienes multi-component random copolymer elastomers after vulcanization.

[0126]

[0127] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, characterized in that, The elastomer is formed by copolymerization and hydrogenation of at least one conjugated diene monomer and at least one bio-based terpene monomer, with a degree of hydrogenation of 45-52%, a number-average molecular weight of 10,000-500,000 g / mol, a molecular weight distribution of 1.9-3.2, a molar content of 10-90% for conjugated diene polymer units, and a molar content of 10-90% for bio-based terpene polymer units. The conjugated diene monomer is isoprene or 1,3-butadiene, and the bio-based terpene monomer is β-myrcene or β-farnesene; The glass transition temperature range is -80~0℃, the tan δ value at 0℃ is 0.7~1.3, the tear strength is >28 N / mm, the elongation at break is >520%, the Shore hardness A is >40, the heat distortion temperature is >80℃, and the embrittlement temperature is <-35℃.

2. The elastomer according to claim 1, characterized in that, The glass transition temperature range is -55~-19℃, the tan δ value at 0℃ is 0.96~1.21, the tear strength is >32 N / mm, the elongation at break is >560%, the Shore hardness A is >51, the heat distortion temperature is >96℃, and the embrittlement temperature is <-43℃.

3. The method for preparing the elastomer according to claim 1 or 2, characterized in that, The method described: (1) A multi-component random copolymer was prepared by copolymerization of conjugated diene monomer and bio-based terpene monomer; (2) The copolymer solution was prepared by dissolving the multi-component random copolymer in a solvent. The Ziegler-Natta hydrogenation reaction system was used. Under an argon atmosphere, the copolymer solution, catalyst and co-catalyst were added to a dry high-temperature reactor in sequence. The gas in the reactor was replaced three times with hydrogen. The reaction was carried out for 1 to 3 hours at a reactor speed of 100 to 1000 rpm, a hydrogenation reaction pressure of 1 to 3 MPa, and a temperature of 10 to 40 °C to obtain a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer. Alternatively, a metallocene hydrogenation reaction system can be used. Under an argon atmosphere, a copolymer solution and a bis(titanium)-based / alkylaluminum / lithium-based metal compound composite catalyst are sequentially added to a dry, high-temperature reactor. The gas in the reactor is replaced three times with hydrogen. The reactor rotation speed is adjusted to 100-1500 rpm, the hydrogenation reaction pressure is 0.1-1.5 MPa, the temperature is raised to 10-60°C, and the reaction is carried out for 1-2 hours to obtain a semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer.

4. The method according to claim 3, characterized in that, Step (1) Copolymerization is carried out using anionic polymerization, cationic polymerization, free radical polymerization or coordination polymerization.

5. The method according to claim 4, characterized in that, The specific process of using anionic polymerization: Copolymerization is initiated under anhydrous and oxygen-free conditions, with organoalkali metals as initiators and / or organoaluminum compounds as cocatalysts.

6. The method according to claim 5, characterized in that, The organoalkali metal is one or more of the following: n-butyllithium, sec-butyllithium, tert-butyllithium, tert-butoxide lithium, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, phenyllithium, benzyllithium, and naphthol. The organoaluminum compound is abbreviated as AB, where A represents one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, dichlorodiethylaluminum, dichloroethylaluminum, or sesquiethylaluminum chloride, and B represents one or more of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2-tert-butylphenol, or 2,6-di-tert-butyl-4-ethylphenol. The reaction temperature is -50 to 70°C, and the reaction time is 10 to 360 min.

7. The method according to claim 6, characterized in that, The reaction temperature is 30~50℃, and the reaction time is 30~120min.

8. The method according to claim 4, characterized in that, Coordination polymerization methods include iron coordination polymerization, Ziegnera-type catalytic system polymerization, cationic lutetium coordination complex polymerization with β-diaminosulfonate as ligand, rare earth lanthanide catalytic polymerization, [OSSO] type titanium complex polymerization, semi-sandwich scandium complex polymerization, and cobalt catalytic system polymerization.

9. The method according to claim 8, characterized in that, The specific process of using iron coordination polymerization: Under anhydrous and oxygen-free conditions, an iron catalyst, a co-catalyst, a conjugated diene monomer, a bio-based terpene monomer, and a solvent are added to the reactor, and the polymerization reaction is carried out under stirring at -30 to 100°C for 10 to 120 minutes.

10. The method according to claim 9, characterized in that, The reaction temperature is -20~30℃, and the reaction time is 30min.

11. The method according to claim 9, characterized in that, The iron catalyst can be any one of the following structural formulas: 。 12. The method according to claim 3, characterized in that, In step (2), the concentration of the copolymer solution is 10 wt%, and the solvent of the copolymer solution is one or more of toluene, xylene, n-hexane, and cyclohexane.

13. The method according to claim 3, characterized in that, In the Ziegler-Natta hydrogenation reaction system, the catalyst is one or more of palladium dichloride, platinum dichloride, platinum tetrachloride, vanadium trichloride, cobalt chloride, titanium tetrachloride, nickel chloride, and nickel naphthenate. The co-catalyst is an organometallic compound of a metal from Group IA to Group IIIA. The mass ratio of copolymer to catalyst in the copolymer solution is (1~500):1, and the molar ratio of catalyst to co-catalyst is 1:(1~9).

14. The method according to claim 13, characterized in that, The catalyst is nickel naphthenate, and the co-catalyst is one or more of aluminum chloride, diethylaluminum chloride, tri-n-hexylaluminum, aluminum tert-butoxide, aluminum nitrate, dimethylaluminum chloride, diisobutylaluminum hydride, and methylaluminoxane.

15. The method according to claim 3, characterized in that, The bis-titanium in the metallocene hydride reaction system includes bis-titanium dichlorodi ...

16. The method according to claim 15, characterized in that, Alkyl aluminum is triisobutylaluminum, and lithium-based metal compounds are lithium hydride.

17. An elastomer possessing high mechanical properties, anti-slip properties, and resistance to deformation, characterized in that, It is formed by vulcanization of the elastomer described in claim 1 or 2.

18. The elastomer with high mechanical properties, anti-slip properties, and resistance to deformation as described in claim 17, characterized in that, After vulcanization, the elastomer has a Shore hardness A > 40, an elongation at break > 300%, and a tear strength > 20 N / mm.

19. The method for preparing the elastomer according to claim 17 or 18, characterized in that, The method described: Weigh out 100 parts by weight of semi-hydrogenated bio-based terpene and conjugated diene multi-component random copolymer elastomer, 5-70 parts of carbon black, 1-4 parts of vulcanization accelerator, 0.1-10 parts of sulfur, 1-8 parts of zinc oxide, 1-10 parts of zinc stearate, 0.5-5 parts of antioxidant and 1-20 parts of filler oil, mix and then knead and vulcanize to obtain the product.

20. The method according to claim 19, characterized in that, The carbon black is one or more of N110 and N320; the vulcanization accelerator is one or more of NS, NA-22, NOBS, CZ, and DCBS; the antioxidant is one or more of quinoline, p-phenylenediamine, or naphthylamine; and the filler oil is one or more of paraffin oil, naphthenic oil, or aromatic oil.

21. The application of the elastomer according to claim 17 or 18 in the fields of industrial materials, building materials and consumer goods.

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