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

Abstract

A hydrogenated conjugated diene and bio-based terpene multivariate random copolymer, and a preparation method and application thereof. The present application belongs to the field of olefin catalytic polymerization and hydrogenation. The purpose of the present application is to solve the problem of insufficient raw material supply in the POE industry and to fill the gap in the research of 1,3-diene hydrogenates. The copolymer of the present application is copolymerized and hydrogenated from at least one of the conjugated diene monomers and at least one of the bio-based terpene monomers, the molar content of the conjugated diene polymerization unit is 10% to 90%, the molar content of the bio-based terpene polymerization unit is 10% to 90%, and the hydrogenation degree is 88% to 99.9%. The copolymer of the present application is used for producing solar photovoltaic film, thin film, automobile accessories, medical packaging material, daily necessities and toys.

Description

Technical Field

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

[0002] POE generally refers to copolymers of ethylene and propylene or other α-olefins (such as 1-octene), which are solution polymerized using a metallocene catalytic system at temperatures above the polymer's melting point. Compared to general polyolefins, POE has longer side chains in its molecular chain, resulting in the simultaneous existence of crystalline and amorphous phases, thus producing unique processing characteristics—exhibiting the high elasticity of rubber while being processed and molded using thermoplastic plastics processes. Furthermore, considering the bonding of POE itself, because the molecular chain is mostly composed of saturated single bonds, it possesses excellent aging resistance and corrosion resistance.

[0003] Currently, POE is in high demand in downstream applications, exhibiting a trend towards diversification, differentiation, and high-end development, primarily in photovoltaic films, automotive materials, packaging, foamed shoe materials, home appliances, and wires and cables. However, the development of POE-related industries still faces challenges such as insufficient raw material supply and immature polymerization processes, requiring urgent solutions.

[0004] 1,3-dienes are a class of widely available and abundant olefin monomers, and some, such as myrcene and farnesene, are renewable resources. While related catalytic polymerization technologies are relatively mature, research on the applications of hydrogenated polymer products is still unsystematic and has not yet become a major research focus, especially regarding bio-based terpenes such as myrcene and farnesene, for which hydrogenation technologies containing these two monomers are rarely reported. To address these issues, it is necessary to develop a catalytic system and subsequent catalytic hydrogenation process to obtain a hydrogenated polymer with POE properties from 1,3-dienes. Summary of the Invention

[0005] The purpose of this invention is to address the raw material supply shortage encountered by the POE industry and to fill the gap in research on 1,3-diene hydrides, by providing a hydrogenated conjugated diene and bio-based terpene multi-component random copolymer, its preparation method, and its application.

[0006] The technical solution of the present invention is as follows:

[0007] One objective of this invention is to provide a hydrogenated conjugated diene and bio-based terpene multi-component random copolymer, wherein the copolymer is formed by copolymerization and hydrogenation of at least one conjugated diene monomer and at least one bio-based terpene monomer, and the general formula of the conjugated diene monomer is C0. n H 2n-2For n≥4, the general formula for bio-based terpene monomers is (C5H8). n n≥2, the molar content of conjugated diene polymer units is 10%–90%, the molar content of bio-based terpene polymer units is 10%–90%, and the degree of hydrogenation is 90%–99.9%.

[0008] Preferably, the conjugated diene monomers include 1,3-butadiene, isoprene, 1,5-hexadiene, and 1,7-octadiene, and the bio-based terpene monomers include limonene, α-pinene, β-pinene, α-myrcene, β-myrcene, α-farnesene, and β-farnesene.

[0009] More preferably, the conjugated diene monomer is isoprene or 1,3-butadiene, and the bio-based terpene monomer is β-myrcene or β-farnesene.

[0010] Preferably, the copolymer has a number-average molecular weight of 1.0–500,000 g / mol, a molecular weight distribution of 1.0–5.0, a glass transition temperature of -80℃–20℃, a Shore hardness A > 40, a resilient modulus > 20%, an elongation at break > 600%, a tear strength > 20 N / mm, and a volume resistivity > 0.6 × 10⁻⁶. 18 Ω·cm, melting point 55℃~80℃, melt index 60~80g / 10min, heat distortion temperature >125℃, light transmittance 380-1100nm >89%, water vapor transmittance <3.5%, low-temperature notched impact strength (-30℃) >59kJ / m 2 Notched impact strength of cantilever beam > 70 kJ / m 2 .

[0011] More preferably, the copolymer has a molecular weight distribution of 1.4–3.1, a degree of hydrogenation of 95%–99%, a glass transition temperature range of -68℃ to -25℃, a Shore hardness A > 52, a resilient modulus > 23%, an elongation at break > 650%, a tear strength > 27 N / mm, and a volume resistivity > 0.76 × 10⁻⁶. 18 Ω·cm, melting point 62℃~69℃, melt index 66~76g / 10min, heat distortion temperature >132℃, light transmittance of 380-1100nm >92%, water vapor transmittance <2.8%, low-temperature notched impact strength (-30℃) >62kJ / m 2 The notched impact strength of the cantilever beam is >76kJ / m. 2 .

[0012] A second objective of this invention is to provide a method for preparing a multi-component random copolymer of hydrogenated conjugated diene and bio-based terpene, the method comprising the following steps:

[0013] (1) A multi-component random copolymer was prepared by copolymerizing conjugated diene monomers and bio-based terpene monomers;

[0014] (2) Dissolve the multi-component random copolymer in a solvent to obtain a copolymer solution, and then hydrogenate it using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a hydrogenated conjugated diene and bio-based terpene multi-component random copolymer.

[0015] Preferably, 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.

[0016] 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.

[0017] When the preparation of multi-component random copolymers is carried out using 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 carried out under stirring at -30℃ to 100℃ for 10 min to 120 min. More preferably, the reaction temperature is -20℃ to 30℃, and the reaction time is 30 min.

[0018] Preferably, the iron catalyst is any one of the following structural formulas:

[0019]

[0020] When anionic polymerization is used to prepare multi-component random copolymers, 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.

[0021] Alternatively, under anhydrous and oxygen-free conditions, organoalkali metals can be used as initiators and organoaluminum compounds as co-catalysts to initiate the copolymerization of conjugated diene monomers and bio-based terpene monomers.

[0022] 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 can be 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.

[0023] Preferably, the reaction temperature is -50℃ to 70℃ and the reaction time is 10 min to 360 min; more preferably, the reaction temperature is 30℃ and the reaction time is 30 min.

[0024] Preferably, the concentration of the copolymer solution in step (2) is 10 wt%.

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

[0026] Preferably, the specific hydrogenation process in step (2) using the Ziegler-Natta hydrogenation reaction system is as follows:

[0027] Under an argon atmosphere, the copolymer solution, catalyst, and co-catalyst are added sequentially to a dry, high-temperature reactor. The gas in the reactor is replaced three times with hydrogen. The reactor rotation speed is adjusted to 100–1000 rpm, the hydrogenation reaction pressure is 1–5 MPa, the temperature is raised to 95°C–120°C, and the reaction is carried out for 1–5 hours.

[0028] More preferably, the catalyst is one or more of nickel sulfate, nickel chloride, nickel nitrate, or nickel naphthenate; the co-catalyst is an organometallic compound of a metal from Group IA to Group IIIA, more preferably one or more of trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum hydride.

[0029] More preferably, the mass ratio of the copolymer to the catalyst in the copolymer solution is (1-500):1; the molar ratio of the catalyst to the co-catalyst is 1:(1-20).

[0030] Preferably, 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.

[0031] More preferably, the specific process of hydrogenation using a di-titanium / alkylaluminum / lithium-based metal compound system is as follows:

[0032] 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 gas in the reactor was replaced three times with hydrogen. The reactor rotation speed was adjusted to 100–1000 rpm, the hydrogenation reaction pressure was 1.6–2.5 MPa, the temperature was raised to 30°C–100°C, and the reaction was carried out for 1–5 hours.

[0033] More preferably, 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; and the lithium metal compound is one or more of lithium methoxide, lithium ethoxide, and lithium phenylene.

[0034] More 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:(1-8); and the molar ratio of the diacetic titanium to the lithium metal compound is 1:(1-10).

[0035] The third objective of this invention is to provide an application of a hydrogenated conjugated diene and bio-based terpene multi-component random copolymer in the fields of solar photovoltaic films, automotive parts, medical packaging materials, building materials, daily necessities and toys.

[0036] The advantages of this invention compared to existing technologies are:

[0037] (1) This invention creatively proposes to first obtain a copolymer of conjugated diene and bio-based terpene through an iron-based coordination polymerization system, and then use a corresponding transition metal catalyst as a hydrogenation catalyst to hydrogenate the double bonds of the copolymer, ultimately obtaining a hydrogenated conjugated diene-bio-based terpene copolymer elastomer material. The saturated single bond ratio of this material's molecular chain reaches over 90%, and its weather resistance, mechanical strength, and ductility are all excellent, possessing the properties of POE and having a certain degree of substitutability for POE. At the same time, because this hydrogenated material has a longer side chain, it has better impact resistance than POE. Due to various factors such as the technical barriers of catalysts, the supply of raw material α-olefins, and the lack of polymerization processes, China has not yet completely broken free from its dependence on POE products. This invention creatively proposes a method for this novel hydrogenation material, which can alleviate the dependence on foreign POE products and help break the monopoly of POE.

[0038] (2) The polymerization route proposed in this invention has the advantages of readily available raw materials, simple operation, and environmentally friendly components. The system has high catalytic activity and the monomer conversion rate can reach more than 90%. At the same time, the hydrogenation process is optimized, which further reduces the hydrogenation cost and the overall hydrogenation degree of the polymer reaches more than 95%. Attached Figure Description

[0039] Figure 1 The binary random copolymer obtained in step (1) of Example 1 1 H NMR spectrum;

[0040] Figure 2 The hydrogenated product obtained in step (2) of Example 1 1 H NMR spectrum;

[0041] Figure 3 The GPC spectrum of the hydrogenated product obtained in step (2) of Example 1;

[0042] Figure 4 The image shows the DSC spectrum of the hydrogenated product obtained in step (2) of 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 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.

[0044] In this invention, when equivalents, concentrations, or other values ​​or parameters 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 occurrences) 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] The term "an embodiment" or "embodiment" as used in this invention 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 hydrogenated conjugated diene and bio-based terpene multi-component random copolymer, wherein the copolymer is formed by copolymerization and hydrogenation of at least one conjugated diene monomer and at least one bio-based terpene monomer, and the general formula of the conjugated diene monomer is C2. n H 2n-2 For n≥4, the general formula for bio-based terpene monomers is (C5H8). n n≥2, the molar content of conjugated diene polymer units is 10%–90%, the molar content of bio-based terpene polymer units is 10%–90%, and the degree of hydrogenation is 90%–99.9%.

[0049] Preferably, the conjugated diene monomers include 1,3-butadiene, isoprene, 1,5-hexadiene, or 1,7-octadiene, and the bio-based terpene monomers include limonene, α-pinene, β-pinene, α-myrcene, β-myrcene, α-farnesene, or β-farnesene.

[0050] More preferably, the conjugated diene monomer is isoprene or 1,3-butadiene, and the bio-based terpene monomer is β-myrcene or β-farnesene.

[0051] Preferably, the copolymer has a number-average molecular weight of 1.0–500,000 g / mol, a molecular weight distribution of 1.0–5.0, a glass transition temperature of -80℃–20℃, a Shore hardness A > 40, a resilient modulus > 20%, an elongation at break > 600%, a tear strength > 20 N / mm, and a volume resistivity > 0.6 × 10⁻⁶. 18 Ω·cm, melting point 55℃~80℃, melt index 60~80g / 10min, heat distortion temperature >125℃, light transmittance 380-1100nm >89%, water vapor transmittance <3.5%, low-temperature notched impact strength (-30℃) >59kJ / m 2 Notched impact strength of cantilever beam > 70 kJ / m 2 .

[0052] More preferably, the copolymer has a molecular weight distribution of 1.4–3.1, a degree of hydrogenation of 95%–99%, a glass transition temperature range of -68℃ to -25℃, a Shore hardness A > 52, a resilient modulus > 23%, an elongation at break > 650%, a tear strength > 27 N / mm, and a volume resistivity > 0.76 × 10⁻⁶. 18 Ω·cm, melting point 62℃~69℃, melt index 66~76g / 10min, heat distortion temperature >132℃, light transmittance of 380-1100nm >92%, water vapor transmittance <2.8%, low-temperature notched impact strength (-30℃) >62kJ / m 2 The notched impact strength of the cantilever beam is >76kJ / m. 2 .

[0053] This invention also provides a method for preparing a multi-component random copolymer of hydrogenated conjugated diene and bio-based terpene, the method comprising the following steps:

[0054] (1) A multi-component random copolymer was prepared by copolymerizing conjugated diene monomers and bio-based terpene monomers;

[0055] (2) Dissolve the multi-component random copolymer in a solvent to obtain a copolymer solution, and then hydrogenate it using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a hydrogenated conjugated diene and bio-based terpene multi-component random copolymer.

[0056] Preferably, 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.

[0057] 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, [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. Even 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.

[0058] When the preparation of multi-component random copolymers is carried out by iron coordination polymerization, the specific steps are as follows: under anhydrous and oxygen-free conditions, iron catalyst, co-catalyst, conjugated diene monomer, bio-based terpene monomer and 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, quencher and anti-aging agent are added, and after washing, vacuum drying is carried out to constant weight to obtain multi-component random copolymers of conjugated diene and bio-based terpene.

[0059] More preferably, the reaction temperature is -20℃ to 30℃, and the reaction time is 30 min.

[0060] When using iron coordination polymerization, the iron catalyst can be any one of the following structural formulas:

[0061]

[0062] More preferably, 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 (3-10):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 200-20000:1.

[0063] More preferably, the co-catalyst is a single-component or a two-component catalyst. When the co-catalyst is a single-component catalyst, it is selected from one or more of methylaluminoxane (MAO), dried methylaluminoxane (DMAO), and modified methylaluminoxane (MMAO), and the molar ratio of aluminum to iron in the co-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. Component B is 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.

[0064] When anionic polymerization is used to prepare multi-component random copolymers, 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.

[0065] 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.

[0066] Preferably, the organic alkali metal is one or more selected from lithium n-butyllithium, lithium sec-butyllithium, lithium tert-butyllithium, lithium tert-butoxide, lithium methyllithium, lithium ethyllithium, lithium n-propyllithium, lithium isopropyllithium, lithium phenyllithium, lithium benzyllithium, and lithium naphthyllithium; more preferably, it is one or more selected from lithium n-butyllithium, lithium sec-butyllithium, lithium tert-butyllithium, and lithium n-propyllithium.

[0067] Preferably, the reaction temperature is -50℃ to 70℃ and the reaction time is 10 min to 360 min; more preferably, the reaction temperature is 30℃ and the reaction time is 30 min.

[0068] Preferably, the solvent is one or more of 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 of THF, toluene, ethylbenzene, n-hexane, cyclohexane, ethylene glycol dimethyl ether, and methyl tert-butyl ether.

[0069] Preferably, the organoaluminum compound can 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.

[0070] Preferably, the volume ratio of solvent to comonomer is (1-50):1, more preferably 3:1; the molar ratio of total comonomer to lithium in initiator is (100-50000):1, more preferably 2000:1; and the molar ratio of total comonomer to aluminum in cocatalyst is (13-6250):1, more preferably 250:1.

[0071] When the preparation of multi-component random copolymers is carried out using free radical polymerization, examples include: hydrogen peroxide polymerization, emulsion polymerization, nitroxide radical polymerization (NMP), and reversible addition chain transfer polymerization (RAFT). Among these methods, nitroxide radical polymerization (NMP) and reversible addition chain transfer polymerization are preferred; the most preferred method is reversible addition chain transfer polymerization, with the initiator being one or more of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptanenitrile, azodihydroxyvalerate, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyramidin hydrochloride, and azoisobutylcyanoformamide.

[0072] When cationic polymerization is used to prepare multi-component random copolymers, 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. Among these methods, LASC polymerization is preferred.

[0073] Preferably, the polymerization reaction can be quenched by adding protic compounds such as methanol, methanol solution of acetic acid, or methanol solution of hydrochloric acid, or aqueous solution of acetic acid or hydrochloric acid to the reaction solution.

[0074] Preferably, the concentration of the copolymer solution in step (2) is 10 wt%.

[0075] Preferably, the solvent of the copolymer solution in step (2) is one or more of toluene, xylene, n-hexane, and cyclohexane.

[0076] Preferably, the specific hydrogenation process in step (2) using the Ziegler-Natta hydrogenation reaction system is as follows:

[0077] 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 1–5 MPa, and the temperature was increased to 95–120 °C for 1–5 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 placed in a vacuum oven and dried at room temperature to constant weight to obtain the final hydrogenated conjugated diene and bio-based terpene multi-component random copolymer.

[0078] More preferably, the catalyst is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel naphthenate, most preferably nickel naphthenate; the co-catalyst is an organometallic compound of a metal from Group IA to Group IIIA, more preferably one or more of trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum hydride, most preferably triisobutylaluminum.

[0079] More preferably, 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:(1-20), more preferably 1:5; the hydrogenation reaction temperature is preferably 100℃; the hydrogenation reaction pressure is preferably 3MPa; the rotation speed of the hydrogenation reactor is preferably 600rpm; and the hydrogenation reaction time is preferably 2.5h.

[0080] Preferably, 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.

[0081] More preferably, the specific process of hydrogenation using a di-titanium / alkylaluminum / lithium-based metal compound system is as follows:

[0082] 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 100–1000 rpm, the hydrogenation reaction pressure was 1.6–2.5 MPa, and the temperature was increased to 30–100 °C for 1–5 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 hydrogenated conjugated diene and bio-based terpene multi-component random copolymer.

[0083] More preferably, 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 methoxide, lithium ethoxide, and lithium phenyl, more preferably lithium ethoxide.

[0084] More preferably, the mass ratio of the copolymer to the bis(titanium) in the copolymer solution is (1-6000):1, more preferably 4000:1; the molar ratio of the bis(titanium) to the alkylaluminum compound is 1:(1-8), more preferably 1:4.5; the molar ratio of the bis(titanium) to the lithium-based metal compound is 1:(1-10), more preferably 1:6; the hydrogenation reaction temperature is preferably 50°C; the hydrogenation reaction pressure is preferably 1.7 MPa; the rotation speed of the hydrogenation reactor is preferably 600 rpm; and the hydrogenation reaction time is preferably 1.5 h.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] In the embodiments described below, when amounts, concentrations, or other values ​​or parameters 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 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.

[0089] 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.

[0090] 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 mutually excludes other embodiments.

[0091] 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.

[0092] The mechanical performance testing standard in the following embodiments is GB / T 589-2009;

[0093] The standard for light transmittance testing is ASTM D1003-2021;

[0094] The melt flow index testing standard is: ASTM D 1238;

[0095] The standard for water vapor transmission rate testing is GB / T 1037-2021;

[0096] The standard for testing low-temperature notched impact strength is ISO 179-1:2010.

[0097] The standard for testing the notched impact strength of cantilever beams is: refer to ISO 180-2019;

[0098] The standard for heat deformation temperature testing is: refer to GB / T1634-2019;

[0099] Oximeter: Keithley; Model 6517B, 1000V, 10min.

[0100] Example 1: The preparation method of a hydrogenated conjugated diene-bioterpene multi-component random copolymer in this example is as follows:

[0101] (1) Polymerization: Under an argon atmosphere, anhydrous toluene (24 mL), isoprene (1.4 mL, 14.0 mmol, 1400 equiv.), β-myrcene (1 mL, 6 mmol, 600 equiv.), MAO (5.0 mmol, 500 equiv.), and iron catalyst 1 (1.0 mL, 10 μmol, 1 equiv.) were added sequentially to a 100 mL Schlenk tube. Polymerization was carried out at -20 °C for 30 min. The reaction was then terminated with a mixture of 25 mL of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of 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.

[0102] (2) Hydrogenation: A 10 wt% xylene mother liquor of the copolymer was prepared in a 100 mL Schlenk tube. 50.0 mL of the 10 wt% xylene mother liquor of the copolymer, nickel naphthenate catalyst (14.3 mg, 35.6 μmol, 1 equiv.), and triethylaluminum co-catalyst (0.18 mL, 178 μmol, 5 equiv.) were added sequentially to the Schlenk tube under an argon atmosphere, and the mixture was stirred at 600 rpm for 20 min. The reaction mixture was purged three times with H2, and the pressure inside the reactor was 3 MPa after purging. Stirring was then started, and the hydrogenation temperature was 100℃ for 2.5 h at a rotation speed of 600 rpm. After the reaction was complete, the hydrogenation reactor was cooled to room temperature, depressurized, and allowed to stand for 30.0 min before being opened. Post-processing yielded a white elastomer.

[0103] Example 2: This example differs from Example 1 in that the amount of MAO added in step (1) is changed to (50.0 mmol, 5000 equiv.), and the amount of iron catalyst 1 added is changed to (10.0 ml, 100 μmol, 10 equiv.). Other steps and parameters are the same as in Example 1.

[0104] Example 3: This example differs from Example 1 in that the reaction was carried out in a 500 mL Schlenk tube, and in step (1), the amount of anhydrous toluene added was (240 mL), the amount of isoprene added was (14 mL, 140.0 mmol, 14000 equiv.), and the amount of β-myrcene added was (10 mL, 60 mmol, 6000 equiv.). Other steps and parameters were the same as in Example 1.

[0105] Example 4: This example differs from Example 1 in that the amount of anhydrous toluene added in step (1) is (17 mL), the amount of β-myrcene added is (0.26 mL, 1.6 mmol, 156 equiv.), and the other steps and parameters are the same as in Example 1.

[0106] Example 5: This example differs from Example 1 in that the amount of anhydrous toluene added in step (1) is (25 mL), the amount of isoprene added is (0.16 mL, 1.6 mmol, 156 equiv.), and the amount of β-myrcene added is (2.3 mL, 14 mmol, 1400 equiv.). Other steps and parameters are the same as in Example 1.

[0107] Example 6: This example differs from Example 1 in that the reaction is carried out in a 50 mL Schlenk tube, and the amount of anhydrous toluene added in step (1) is 7.2 mL. Other steps and parameters are the same as in Example 1.

[0108] Example 7: The difference between this example and Example 1 is that the iron catalyst in step (1) is replaced with iron catalyst 7 (1.0 ml, 10 μmol, 1 equiv.), and the other steps and parameters are the same as in Example 1.

[0109] Example 8: This example differs from Example 1 in that the amount of anhydrous toluene added in step (1) is (27 ml), and the bio-based terpene in the comonomer is replaced by β-farnesene (1.7 ml, 6 mmol, 600 equiv.). Other steps and parameters are the same as in Example 1.

[0110] Example 9: This example differs from Example 1 in that the amount of anhydrous toluene added in step (1) is (21 ml), and the conjugated diene in the comonomer is replaced by 1,3-butadiene (1.14 mL, 14.0 mmol, 1400 equiv.). Other steps and parameters are the same as in Example 1.

[0111] Example 10: This example differs from Example 1 in that: the amount of anhydrous toluene added in step (1) is (28 ml), the conjugated diene in the comonomer is replaced by 1,3-butadiene (1.14 mL, 14.0 mmol, 1400 equiv.), and the bio-based terpene is replaced by β-myrcene (1.7 ml, 6 mmol, 600 equiv.). Other steps and parameters are the same as in Example 1.

[0112] Example 11: This example differs from Example 1 in that: anhydrous toluene (28 mL), isoprene (1.4 mL, 14.0 mmol, 1400 equiv.), β-myrcene (0.52 mL, 3 mmol, 300 equiv.), and β-farnesene (0.84 mL, 3 mmol, 300 equiv.) were used, while other steps and parameters were the same as in Example 1.

[0113] Example 12: This example differs from Example 1 in that: anhydrous toluene (25 mL) was used, and the polymer monomer isoprene was replaced with 1,3-butadiene. The amount of 1,3-butadiene added was (1.14 mL, 14.0 mmol, 1400 equiv.). Other steps and parameters were the same as in Example 1.

[0114] Example 13: This example differs from Example 1 in that: anhydrous toluene (25 mL), isoprene (1.08 mL, 10.8 mmol, 1080 equiv.), 1,3-butadiene (0.88 mL, 10.8 mmol, 1080 equiv.), β-myrcene (0.2 mL, 1.2 mmol, 120 equiv.), and β-farnesene (0.34 mL, 1.2 mmol, 120 equiv.) are used. Other steps and parameters are the same as in Example 1.

[0115] Example 14: This example differs from Example 1 in that the copolymerization method in step (1) uses anionic polymerization. Specific steps are as follows:

[0116] (1) Polymerization: Under an argon atmosphere, anhydrous toluene (7.2 mL) and i-BuAl(BHT) were added sequentially to a 100 mL Schlenk tube. 1.9 Aluminum reagent (5 mL, 1.6 mmol, 8 equiv.), initiator sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.), isoprene (1.4 mL, 14.0 mmol, 1400 equiv.), and β-myrcene (1 mL, 6 mmol, 600 equiv.) were polymerized at 30 °C for 30 min. The reaction was then terminated with a mixture of 25 mL of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of 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. Other steps and parameters were the same as in Example 1.

[0117] Example 15: This example differs from Example 1 in that the hydrogenation reaction system in step (2) is replaced with a bis(titanium)-based / alkylaluminum / lithium-based metal compound system. Specific steps:

[0118] (2) Hydrogenation: A 10 wt% xylene mother liquor of the copolymer was prepared in a 100 mL Schlenk tube. The reactor was dried and heated to 70 °C. Under an argon atmosphere, 50.0 mL of the 10 wt% xylene mother liquor of the copolymer, 0.31 mg, 1.25 μmol, 1 equiv. of titanium dichlorophenoxyacetate catalyst, 0.16 mL, 162 μmol, 4.5 equiv. of triisobutylaluminum co-catalyst, and 0.21 mL, 7.5 μmol, 6 equiv. of lithium ethoxide were added sequentially. The mixture was stirred at 600 rpm for 20 min. The reactor was purged with H2 three times, and the pressure inside the reactor was 1.7 MPa after purging. The stirring was then started, the hydrogenation temperature was 50 °C, the hydrogenation time was 1.5 h, and the stirring speed was 600 rpm. After the reaction was completed, the hydrogenation reactor was cooled to room temperature, depressurized, and allowed to stand for 30.0 min before being opened. Post-processing was performed to obtain a white elastomer. Other steps and parameters were the same as in Example 1.

[0119] Table 1. Test data of hydrogenated conjugated dienes and bio-based terpenoid multi-component random copolymer elastomers in Examples 1-8

[0120]

[0121] Table 2 Test data of hydrogenated conjugated dienes and bio-based terpenoid multi-component random copolymer elastomers in Examples 9-15

[0122]

[0123]

[0124] 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 hydrogenated conjugated diene and bio-based terpene multi-component random copolymer, characterized in that, The copolymer is formed by copolymerization and hydrogenation of at least one conjugated diene monomer and at least one bio-based terpene monomer, wherein the general formula of the conjugated diene monomer is C1. n H 2n-2 For n≥4, the general formula for bio-based terpene monomers is (C5H8). n n≥2, the molar content of conjugated diene polymer units is 10%~90%, the molar content of bio-based terpene polymer units is 10%~90%, and the degree of hydrogenation is 90%~99.9%; The copolymer has a number-average molecular weight of 10,000–500,000 g / mol, a molecular weight distribution of 1.0–5.0, a glass transition temperature of -80℃ to 20℃, a Shore hardness A > 40, a resilient modulus > 20%, an elongation at break > 600%, a tear strength > 20 N / mm, and a volume resistivity > 0.6 × 10⁻⁶. 18 Ω·cm, melting point 55℃~80℃, melt index 60~80 g / 10min, heat distortion temperature >125℃, light transmittance 380-1100nm >89%, water vapor transmittance <3.5%, notched impact strength at -30℃ >59 kJ / m 2 Notched impact strength of cantilever beam > 70 kJ / m 2 .

2. The copolymer according to claim 1, characterized in that, Conjugated diene monomers include 1,3-butadiene, isoprene, 1,5-hexadiene, and 1,7-octadiene, while bio-based terpene monomers include limonene, α-pinene, β-pinene, α-myrcene, β-myrcene, α-farnesene, and β-farnesene.

3. The copolymer according to claim 2, characterized in that, The conjugated diene monomer is isoprene or 1,3-butadiene, and the bio-based terpene monomer is β-myrcene or β-farnesene.

4. The copolymer according to claim 1, characterized in that, Molecular weight distribution: 1.4–3.1; Degree of hydrogenation: 95%–99%; Glass transition temperature range: -68℃ to -25℃; Shore hardness A: >52; Resilient modulus: >23%; Elongation at break: >650%; Tear strength: >27 N / mm; Volume resistivity: >0.76 × 10⁻⁶. 18 Ω·cm, melting point 62℃~69℃, melt index 66~76 g / 10min, heat distortion temperature >132℃, light transmittance 380-1100nm >92%, water vapor transmittance <2.8%, notched impact strength at -30℃ >62 kJ / m 2 Notched impact strength of cantilever beam > 76 kJ / m 2 .

5. A method for preparing the copolymer according to any one of claims 1-4, 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) Dissolve the multi-component random copolymer in a solvent to obtain a copolymer solution, and then hydrogenate it using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a hydrogenated conjugated diene and bio-based terpene multi-component random copolymer.

6. The method according to claim 5, characterized in that, Step (1) Copolymerization is carried out using anionic polymerization, cationic polymerization, free radical polymerization or coordination polymerization.

7. The method according to claim 6, 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.

8. The method according to claim 7, 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℃, and the reaction time is 10 min to 360 min.

9. The method according to claim 8, characterized in that, The reaction temperature was 30℃ and the reaction time was 30 min.

10. The method according to claim 6, 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.

11. The method according to claim 10, 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 min.

12. The method according to claim 11, characterized in that, The reaction temperature is -20℃ to 30℃, and the reaction time is 30 min.

13. The method according to claim 11, characterized in that, The iron catalyst can be any one of the following structural formulas: 。 14. The method according to claim 5, 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.

15. The method according to claim 5, characterized in that, The Ziegler-Natta hydrogenation reaction process in step (2) is as follows: Under an argon atmosphere, the copolymer solution, catalyst, and co-catalyst are added sequentially to a dry, high-temperature reactor. The gas in the reactor is replaced three times with hydrogen. The reaction is carried out for 1 to 5 hours at a reactor rotation speed of 100 to 1000 rpm, a hydrogenation reaction pressure of 1 to 5 MPa, and a temperature of 95°C to 120°C.

16. The method according to claim 15, characterized in that, The catalyst is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel naphthenate, and the co-catalyst is an organometallic compound of a metal from Group IA to Group IIIA. The mass ratio of the copolymer to the catalyst in the copolymer solution is (1 ~ 500):1, and the molar ratio of the catalyst to the co-catalyst is 1:(1 ~ 20).

17. The method according to claim 16, characterized in that, The catalyst is nickel naphthenate, and the co-catalyst is one or more of trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum hydride.

18. The method according to claim 5, characterized in that, The metallocene hydride 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.

19. The method according to claim 18, characterized in that, The specific process of hydrogenation using the bis(titanium)crylonitrile / alkylaluminum / lithium-based metal compound system is as follows: 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 gas in the reactor was replaced three times with hydrogen. The reactor rotation speed was 100-1000 rpm, the hydrogenation reaction pressure was 1.6-2.5 MPa, the temperature was raised to 30℃-100℃, and the reaction was carried out for 1-5 hours.

20. The method according to claim 19, characterized in that, Dichlorodicyclopentadiene includes dichlorodicyclopentadiene, wherein the alkyl aluminum is one or more of trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, dichlorodiethylaluminum, dichloroethylaluminum, and diisobutylaluminum hydride, and the lithium metal compound is one or more of lithium methoxide, lithium ethoxide, and lithium phenylene. The mass ratio of the copolymer to the dichlorodicyclopentadiene in the copolymer solution is (1~6000):1, the molar ratio of the dichlorodicyclopentadiene to the alkyl aluminum compound is 1:(1~8), and the molar ratio of the dichlorodicyclopentadiene to the lithium metal compound is 1:(1~10).

21. The copolymer according to any one of claims 1-4 is used in the production of solar photovoltaic films, automotive parts, medical packaging materials, building materials, daily necessities and toys.

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