A hydrogenated bio-based terpene-based two-component random copolymer elastomer, and a preparation method and application thereof
Hydrogenated bio-based terpene binary random copolymer elastomers were prepared by copolymerizing and hydrogenating bio-based monoterpenes and sesquiterpenes, which solved the bottleneck of POE industry development and the problem of low performance of bio-based materials, and realized the industrial application of high-performance hydrogenated terpene polymers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
- Filing Date
- 2024-08-29
- Publication Date
- 2026-05-19
AI Technical Summary
The development of the POE industry in the current technology is facing bottlenecks. The overall performance of bio-based materials is not high and cannot meet the needs of high-end consumer products. Furthermore, research on hydrogenated polymers has not involved hydrogenated terpene polymers.
Hydrogenated bio-based terpene binary random copolymer elastomers were prepared by copolymerization and hydrogenation of bio-based monoterpenes and sesquiterpenes. Hydrogenation was carried out using Ziegler-Natta or metallocene hydrogenation reaction systems to obtain copolymers without carbon-hydrogen double bonds, which have long side chains and high degree of hydrogenation.
The prepared hydrogenated bio-based terpene binary random copolymer elastomer has good light transmittance, aging resistance and high elongation at break, excellent mechanical strength and ductility, and is suitable for hot melt adhesive films and hot melt adhesives in multiple fields. It reduces the cost of hydrogenation and is suitable for industrial production.
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Figure CN119060253B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of olefin catalytic polymerization and hydrogenation, specifically relating to a hydrogenated bio-based terpene binary random copolymer elastomer, its preparation method, and its application. Background Technology
[0002] With the depletion of fossil fuels and increasing environmental awareness, the timely development of new sustainable bio-based energy sources and their use in synthesizing polymer materials to replace petroleum derivatives has become increasingly important. Bio-based terpenes are a currently popular type of sustainable bio-based energy. They are a class of natural molecular biomass rich in hydrocarbons, and terpenes are a major component of the resins produced by many plants, such as pine and coniferous trees. Most terpenes possess a basic alicyclic structure and the isoprene basic unit. They can be classified according to the number of isoprene molecules they contain, such as hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, disesquiterpenes, and triterpenes. These terpenes can be used as monomers in various polymerization reactions.
[0003] In modern society, the public's demand for high-end lifestyles and daily chemical products has increased. Currently, in my country, the consumption of POE elastomers in various applications such as membranes, automotive parts, medical packaging materials, wires and cables, daily necessities, toys, and stretchable or flexible energy storage devices is gradually increasing. The main polymer material used to produce these consumer products is POE. POE is a copolymer of ethylene and octene, with no carbon-hydrogen double bonds in its molecular chain and relatively long side chains. While my country is a major consumer of POE, the development of POE-related products in my country is not yet complete and still faces serious challenges, requiring a rapid resolution to the current development difficulties. Current research on hydrogenated polymers has not yet involved hydrogenated terpene polymers, indicating high research potential and development prospects. Therefore, in response to the increasingly serious global environmental problems, it is necessary to develop a new type of bio-based material to alleviate the domestic demand for POE elastomers, while fully utilizing existing bio-based resources. Summary of the Invention
[0004] The purpose of this invention is to address the technical problems of bottlenecks in the development of the POE industry and the low overall performance of bio-based materials, and to provide a hydrogenated bio-based terpene binary random copolymer elastomer, its preparation method, and its application.
[0005] The technical solution of the present invention is as follows:
[0006] One objective of this invention is to provide a hydrogenated bio-based terpene binary random copolymer elastomer, wherein the hydrogenated bio-based terpene binary random copolymer elastomer is formed by copolymerization and hydrogenation of bio-based monoterpenes and bio-based sesquiterpenes, wherein the molar content of monoterpene polymer units is 5-95%, the molar content of sesquiterpene polymer units is 5-95%, the degree of hydrogenation is 90%-99.9%, the number average molecular weight is 1.0-500,000 g / mol, and the molecular weight distribution is 1.0-5.0.
[0007] Preferably, the monoterpenes are one or more of geraniol, limonene, α-myrcene, β-myrcene, β-citronellol, citral, and menthol, and the sesquiterpenes are one or more of juniperene, α-farnesene, β-farnesene, cedrene, and caryophyllene.
[0008] More preferably, the monoterpene is β-myrcene and the sesquiterpene is β-farnesene.
[0009] Preferably, the hydrogenated bio-based terpene binary random copolymer elastomer has a molar content of 10-90% for monoterpene polymer units, a molar content of 10-90% for sesquiterpene polymer units, a degree of hydrogenation of 96-99%, and a molecular weight distribution of 1.9-3.1.
[0010] Preferably, the glass transition temperature range of the hydrogenated bio-based terpene binary random copolymer elastomer is -80 to -50°C.
[0011] More preferably, the glass transition temperature range of the hydrogenated bio-based terpene binary random copolymer elastomer is -69 to -60°C.
[0012] Preferably, the hydrogenated bio-based terpene binary random copolymer elastomer has an elongation at break >800% and a volume resistivity >0.6×10⁻⁶. 18 Ω·cm, melt flow index of 65–85 g / 10 min, transmittance of 85–99% at 380–1100 nm, water vapor transmittance of 2–3.9%, and low-temperature notched impact strength of 50–70 KJ / m at -30℃. 2 The notched impact strength of the cantilever beam is 10–20 KJ / m. 2 The heat distortion temperature is 130~160℃.
[0013] More preferably, the hydrogenated bio-based terpene binary random copolymer elastomer has an elongation at break >850% and a volume resistivity >0.78×10⁻⁶. 18 Ω·cm, melt flow index 69–76 g / 10 min, transmittance at 380–1100 nm 89–94%, water vapor transmittance 2.5–3.1%, and low-temperature notched impact strength at -30℃ 59–65 KJ / m 2 The notched impact strength of the cantilever beam is 13.7–15.1 KJ / m.2 The heat distortion temperature is 139–151℃.
[0014] The second objective of this invention is to provide a method for preparing a hydrogenated bio-based terpene binary random copolymer elastomer, characterized in that the method comprises:
[0015] (1) A binary random copolymer was prepared by copolymerizing bio-based monoterpenes and bio-based sesquiterpenes;
[0016] (2) The binary random copolymer is dissolved in a solvent to prepare a copolymer solution, and then hydrogenated using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a hydrogenated bio-based terpene binary random copolymer elastomer.
[0017] Preferably, the copolymerization in step (1) is carried out by anionic polymerization, cationic polymerization, free radical polymerization or coordination polymerization.
[0018] More preferably, the specific process of anionic polymerization is as follows:
[0019] Copolymerization is initiated under anhydrous and oxygen-free conditions, with organoalkali metals as initiators and / or organoaluminum compounds as cocatalysts.
[0020] 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 can be abbreviated as AB, where A represents one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, dichlorodiethylaluminum, dichloroethylaluminum, and sesquiethylaluminum chloride, and B represents one or more of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2-tert-butylphenol, and 2,6-di-tert-butyl-4-ethylphenol; the reaction temperature is -50℃ to 70℃, and the reaction time is 10 to 360 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, bio-based monoterpenes and bio-based sesquiterpenes monomers and a solvent are added to the reactor, and the polymerization reaction is carried out under stirring at 0–100°C for 10–120 min.
[0024] More preferably, the iron catalyst is any one of the following structural formulas:
[0025]
[0026] 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.
[0027] Preferably, the Ziegler-Natta hydrogenation reaction process in step (2) is as follows:
[0028] Under an argon atmosphere, a copolymer solution, a mixture of catalyst and co-catalyst are added to a dry, high-temperature reactor. The gas in the reactor is replaced three times with hydrogen. The reactor speed is adjusted to 200–600 rpm, the hydrogenation reaction pressure is 1–4 MPa, the temperature is raised to 45–70 °C, and the reaction is carried out for 1–3 hours.
[0029] More preferably, the catalyst is one or more of titanium dioxide, titanium sulfate, titanium hydroxide, nickel naphthenate, nickel bromide, nickel cobaltide, and nickel fluoride, 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 (1-300):1, and the molar ratio of the catalyst to the co-catalyst is 1:(1-10).
[0030] More preferably, the catalyst is titanium sulfate or nickel naphthenate, and the co-catalyst is one or more of aluminum acetate, aluminum hydroxide, sesquiethyl aluminum chloride, DMAO, and MMAO.
[0031] 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.
[0032] More preferably, the specific process of hydrogenation using a bis(titanium)-aluminum / alkylaluminum / lithium-based metal compound system is as follows:
[0033] 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 200–800 rpm, the hydrogenation reaction pressure was 2.5–3.0 MPa, the temperature was raised to 50–80 °C, and the reaction was carried out for 0.1–1.5 h.
[0034] More preferably, the catalyst diacenetimonide includes diacenetimonide dichlorodi ...
[0035] The third objective of this invention is to provide an application of the above-mentioned hydrogenated bio-based terpene binary random copolymer elastomer in the preparation of hot melt adhesives and their membrane products for use in photovoltaic solar energy and batteries, automotive interiors, clothing, footwear, electronics, wall coverings, construction, filtration, or pharmaceutical fields.
[0036] The advantages of this invention compared to existing technologies are:
[0037] (1) This invention uses bio-based monoterpene monomers with a glass transition temperature below -65℃ and bio-based sesquiterpene monomers with a glass transition temperature below -70℃ to randomly copolymerize a binary random copolymer. The resulting binary random copolymer is then hydrogenated to obtain a hydrogenated bio-based terpene binary random copolymer elastomer that does not contain carbon-hydrogen double bonds and has relatively long side chains. This hydrogenated product exhibits good light transmittance, aging resistance, and high elongation at break, and can be used to produce hot melt adhesive films and hot melt adhesives for use in photovoltaic solar cells and batteries, automotive interiors, clothing, footwear, electronics, wall coverings, construction, filtration, and pharmaceuticals.
[0038] (2) The hydrogenated bio-based terpene binary random copolymer elastomer of the present invention has a carbon-carbon single bond ratio of over 90%, exhibiting excellent weather resistance, mechanical strength, and ductility. Structurally similar to POE elastomer, it contains longer side chains, thus possessing superior impact resistance compared to POE. It also shares excellent processing and performance characteristics with POE. Furthermore, the longer side chains result in stronger elastic deformation recovery.
[0039] (3) 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. The overall hydrogenation degree of the polymer reaches more than 95%, which is suitable for industrial production and reduces the dependence on POE products. Attached Figure Description
[0040] Figure 1 The bio-based terpene binary random copolymer obtained in Example 1 1 H NMR spectrum;
[0041] Figure 2 The hydrogenated bio-based terpene binary random copolymer elastomer obtained in Example 1 1 H NMR spectrum;
[0042] Figure 3 The GPC spectrum of the hydrogenated bio-based terpene binary random copolymer elastomer obtained in Example 1 is shown below.
[0043] Figure 4 The image shows the DSC spectrum of the hydrogenated bio-based terpene binary random copolymer elastomer obtained in Example 1. Detailed Implementation
[0044] This invention provides a hydrogenated bio-based terpene binary random copolymer elastomer, wherein the hydrogenated bio-based terpene binary random copolymer elastomer is formed by copolymerization and hydrogenation of bio-based monoterpenes and bio-based sesquiterpenes, wherein the molar content of monoterpene polymer units is 5-95%, the molar content of sesquiterpene polymer units is 5-95%, the degree of hydrogenation is 90%-99.9%, the number average molecular weight is 1.0-500,000 g / mol, and the molecular weight distribution is 1.0-5.0.
[0045] Preferably, the monoterpenes are one or more of geraniol, limonene, α-myrcene, β-myrcene, β-citronellol, citral, and menthol, and more preferably β-myrcene; the sesquiterpenes are one or more of juniperene, α-farnesene, β-farnesene, cedrene, and caryophyllene, and more preferably β-farnesene.
[0046] Preferably, the hydrogenated bio-based terpene binary random copolymer elastomer has a molar content of 10-90% for monoterpene polymer units, a molar content of 10-90% for sesquiterpene polymer units, a degree of hydrogenation of 96-99%, and a molecular weight distribution of 1.9-3.1.
[0047] Preferably, the glass transition temperature range of the hydrogenated bio-based terpene binary random copolymer elastomer is -80 to -50°C, and more preferably -69 to -60°C.
[0048] Preferably, the hydrogenated bio-based terpene binary random copolymer elastomer has an elongation at break >800% and a volume resistivity >0.6×10⁻⁶. 18 Ω·cm, melt flow index of 65–85 g / 10 min, transmittance of 85–99% at 380–1100 nm, water vapor transmittance of 2–3.9%, and low-temperature notched impact strength of 50–70 KJ / m at -30℃. 2 The notched impact strength of the cantilever beam is 10–20 KJ / m. 2The heat distortion temperature is 130–160℃. More preferably, the hydrogenated bio-based terpene binary random copolymer elastomer has an elongation at break >850% and a volume resistivity >0.78×10⁻⁶. 18 Ω·cm, melt flow index 69–76 g / 10 min, transmittance at 380–1100 nm 89–94%, water vapor transmittance 2.5–3.1%, and low-temperature notched impact strength at -30℃ 59–65 KJ / m 2 The notched impact strength of the cantilever beam is 13.7–15.1 KJ / m. 2 The heat distortion temperature is 139–151℃.
[0049] This invention also provides a method for preparing a hydrogenated bio-based terpene binary random copolymer elastomer, the method comprising the following steps:
[0050] (1) A binary random copolymer was prepared by copolymerizing bio-based monoterpenes and bio-based sesquiterpenes;
[0051] (2) The binary random copolymer is dissolved in a solvent to prepare a copolymer solution, and then hydrogenated using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a hydrogenated bio-based terpene binary random copolymer elastomer.
[0052] Preferably, the preparation of the binary 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.
[0053] 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.
[0054] Preferably, when the preparation of the binary random copolymer is carried out by iron coordination polymerization, the specific steps are as follows: under anhydrous and oxygen-free conditions, iron catalyst, co-catalyst, bio-based monoterpene and bio-based sesquiterpene monomers and solvent are added to the reactor, and the polymerization reaction is stirred at 0 to 100°C for 10 to 120 min.
[0055] Preferably, the iron catalyst is any one of the following structural formulas:
[0056]
[0057] More preferably, the reaction temperature is 0–30°C and the reaction time is 30 min.
[0058] 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 (155-20000):1.
[0059] 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.
[0060] When the preparation of binary random copolymers 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 bio-based monoterpenes and bio-based sesquiterpenes. After reacting at a certain temperature for a certain time, ethanol is added to quench the reaction and obtain the polymer product.
[0061] 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 bio-based monoterpenes and bio-based sesquiterpenes. After reacting at a certain temperature for a certain time, ethanol is added to quench the reaction and obtain the polymer product.
[0062] 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.
[0063] Preferably, the reaction temperature is -50℃ to 70℃ and the reaction time is 10 to 360 min; more preferably, the reaction temperature is 25℃ and the reaction time is 30 min.
[0064] Preferably, 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, the solvent is one or more selected from THF, toluene, ethylbenzene, n-hexane, cyclohexane, ethylene glycol dimethyl ether, and methyl tert-butyl ether.
[0065] Preferably, the organoaluminum compound can be abbreviated as AB, where A represents one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, and sesquiethylaluminum chloride, and B represents one or more of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2-tert-butylphenol, and 2,6-di-tert-butyl-4-ethylphenol, and the molar ratio of A to B is (0.1-2):1.
[0066] Preferably, the volume ratio of solvent to comonomer is 3:1; the molar ratio of total comonomer to lithium in initiator is 1556:1; and the molar ratio of total comonomer to aluminum in cocatalyst is 195:1.
[0067] When the preparation of binary random copolymers is carried out by free radical polymerization, the following methods can be listed: hydrogen peroxide polymerization, emulsion polymerization, nitrile radical polymerization (NMP), reversible addition chain transfer polymerization (RAFT), etc. 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 azoisobutyroxycyanoformamide.
[0068] When cationic polymerization is used to prepare binary random copolymers, examples include: cationic polymerization 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.
[0069] 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.
[0070] Preferably, the concentration of the copolymer solution in step (2) is 10 wt%.
[0071] Preferably, the solvent of the copolymer solution in step (2) is one or more of toluene, xylene, n-hexane, and cyclohexane.
[0072] Preferably, the specific hydrogenation process in step (2) using the Ziegler-Natta hydrogenation reaction system is as follows:
[0073] Under an argon atmosphere, a copolymer solution, a catalyst, and a co-catalyst mixture were added to a dry, high-temperature reactor. The reactor was purged three times with hydrogen. The reactor rotation speed was adjusted to 200–600 rpm, the hydrogenation reaction pressure was 1–4 MPa, and the temperature was raised to 45–70 °C for 1–3 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 placed in a vacuum oven and dried at room temperature to constant weight to obtain the final hydrogenated bio-based terpene binary random copolymer elastomer.
[0074] More preferably, the catalyst is one or more of titanium dioxide, titanium sulfate, titanium hydroxide, nickel naphthenate, nickel bromide, nickel cobaltide, and nickel fluoride, with titanium sulfate or 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 acetate, aluminum hydroxide, sesquiethylaluminum chloride, DMAO, and MMAO, with aluminum hydroxide being the most preferred.
[0075] More preferably, the mass ratio of the copolymer to the catalyst in the copolymer solution is (1-300):1, more preferably 200:1; the molar ratio of the catalyst to the co-catalyst is 1:(1-10), more preferably 1:3.
[0076] More preferably, the hydrogenation reaction temperature is 60°C, the hydrogenation reaction pressure is 1.5 MPa, the rotation speed of the hydrogenation reactor is 500 rpm, and the hydrogenation reaction time is 1.5 h.
[0077] 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.
[0078] More preferably, the specific process of hydrogenation using a di-titanium / alkylaluminum / lithium-based metal compound system is as follows:
[0079] 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 200–800 rpm, the hydrogenation reaction pressure was 2.5–3 MPa, the temperature was raised to 50–80 °C, and the reaction time was 0.1–1.5 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 to obtain the final hydrogenated bio-based terpene binary random copolymer elastomer.
[0080] More preferably, the catalyst, bis(titanium)chlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodimethylaluminum, trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, and diisobutylaluminum hydride, more preferably aluminum chloride; and the lithium metal compound, which is one or more of lithium fluoride, lithium carbonate, lithium phosphate, lithium nitride, lithium hydroxide, and lithium chloride, more preferably lithium hydroxide.
[0081] More preferably, the mass ratio of the copolymer to the bis(titanium) in the copolymer solution is (1-5000):1, more preferably 2500:1; the molar ratio of the bis(titanium) to the alkylaluminum is 1:(1-6), more preferably 1:3; the molar ratio of the bis(titanium) to the lithium-based metal compound is 1:(1-8), more preferably 1:5; the hydrogenation reaction temperature is preferably 60°C; the hydrogenation reaction pressure is preferably 2.5 MPa; the rotation speed of the hydrogenation reactor is preferably 500 rpm; and the hydrogenation reaction time is preferably 1 h.
[0082] 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.
[0083] 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.
[0084] The standard for testing elongation at break in the following examples is GB / T589-2009;
[0085] The standard for light transmittance testing is ASTM D1003-2021;
[0086] The standard for water vapor transmission rate testing is GB / T 1037-2021;
[0087] The standard for testing low-temperature notched impact strength is ISO 179-1:2010.
[0088] The standard for testing the notched impact strength of cantilever beams is: refer to ISO 180-2019;
[0089] The standard for testing heat deformation temperature is: refer to GB / T1634-2019;
[0090] Oximeter: Keithley; Model 6517B, 1000V, 10min.
[0091] Example 1: The preparation method of a hydrogenated bio-based terpene binary random copolymer elastomer in this example is as follows:
[0092] (1) Polymerization: Under an argon atmosphere, anhydrous toluene (12.7 mL), β-farnesene (4 mL, 14 mmol, 1400 equiv.), β-myrcene (0.26 mL, 1.56 mmol, 156 equiv.), MAO reagent (5.0 mmol, 500 equiv.), and iron catalyst 2 (1.0 mL, 10 μmol, 1 equiv.) were added sequentially to a 50 mL Schlenk tube. Polymerization was carried out 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 anti-aging agent. 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 a binary random copolymer.
[0093] (2) Hydrogenation: A 10 wt% xylene mother liquor of the copolymer was prepared in a 100 mL Schlenk tube. The catalyst, nickel naphthenate (25 mg, 62.3 μmol, 1 equiv.), and the co-catalyst, aluminum hydroxide (14.6 mg, 187 μmol, 3 equiv.), were added sequentially to the Schlenk tube under an argon atmosphere, and the mixture was stirred at 500 rpm for 20 mins. The reactor was dried, and 50.0 mL of the xylene mother liquor of the copolymer (10 wt%) and the catalyst and co-catalyst reaction mixture were added under an argon atmosphere. The reactor was purged three times with H2, and after pressurization, the pressure inside the reactor was 1.5 MPa. Stirring was started, and the hydrogenation temperature was 60 °C for 1.5 h at a rotation speed of 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 for post-treatment to obtain a white elastomer.
[0094] Example 2: This example differs from Example 1 in that the amount of MAO reagent added is (50.0 mmol, 5000 equiv.), and the amount of iron catalyst 2 is (10.0 ml, 100 μmol, 10 equiv.). Other steps and parameters are the same as in Example 1.
[0095] Example 3: This example differs from Example 1 in that the reaction was carried out in a 500 mL Schlenk tube, the amount of anhydrous toluene added was (150 mL), the amount of β-farnesene added was (40 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.
[0096] Example 4: This example differs from Example 1 in that the amount of anhydrous toluene added is (6.3 mL), the amount of β-farnesene added is (2 mL, 7 mmol, 700 equiv.), and the amount of β-myrcene added is (1.17 mL, 7 mmol, 700 equiv.). Other steps and parameters are the same as in Example 1.
[0097] Example 5: This example differs from Example 1 in that the amount of anhydrous toluene added is (8.3 mL), the amount of β-farnesene added is (0.45 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.
[0098] Example 6: This example differs from Example 1 in that the reaction is carried out in a 100 mL Schlenk tube, and the amount of anhydrous toluene added is (43 mL). Other steps and parameters are the same as in Example 1.
[0099] Example 7: This example differs from Example 1 in that the iron catalyst is replaced with iron catalyst 1, and the amount added is (1.0 ml, 10 μmol, 1 equiv.). The copolymerization reaction temperature is 0°C. Other steps and parameters are the same as in Example 1.
[0100] Example 8: This example differs from Example 1 in that step (1) copolymerization uses anionic polymerization, and the specific steps are as follows:
[0101] (1) Polymerization: Under an argon atmosphere, anhydrous toluene (13 mL) and i-BuAl(BHT) were added sequentially to a 100 mL reaction flask. 1.9The reaction was carried out with aluminum reagent (5 mL, 1.6 mmol, 8 equiv.), initiator sec-butyllithium (0.15 mL, 0.2 mmol, 1 equiv.), and β-farnesene (4 mL, 14 mmol, 1400 equiv.), and β-myrcene (0.26 mL, 1.56 mmol, 156 equiv.). Polymerization was performed at 25 °C for 30 min, followed by termination with 25 mL of a mixture 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. Other steps and parameters were the same as in Example 1.
[0102] Example 9: 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 hydrogenation system. The specific steps are as follows:
[0103] (2) Hydrogenation: A 10 wt% xylene mother liquor of the copolymer was prepared in a 100 mL Schlenk tube. The hydrogenation 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, the catalyst dichlorodicyclopentadiene (2 mg, 8 μmol, 1 equiv.), and the co-catalysts aluminum chloride (3.2 mg, 24 μmol, 3 equiv.) and lithium hydroxide (0.96 mg, 40 μmol, 5 equiv.) were added. The reactor was purged with H2 three times. The pressure inside the hydrogenation reactor was set to 2.5 MPa. Stirring was started, the hydrogenation reaction temperature was 60 °C, the hydrogenation reaction time was 1 h, and the stirring speed was 500 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. Anhydrous ethanol was added for post-treatment to obtain a white elastomer. Other steps and parameters were the same as in Example 1.
[0104] Table 1. Data parameters of hydrogenated bio-based terpene binary random copolymer elastomers
[0105]
[0106] 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 bio-based terpene binary random copolymer elastomer, characterized in that, The elastomer is synthesized and hydrogenated from bio-based monoterpenes and bio-based sesquiterpenes. The molar content of monoterpenes and sesquiterpenes is 10-90%, the degree of hydrogenation is 96-99%, the number-average molecular weight is 1.0-500,000 g / mol, and the molecular weight distribution is 1.9-3.
1. The glass transition temperature range of the elastomer is -69 to -60℃. The monoterpene is β-myrcene, and the sesquiterpene is β-farnesene; The elastomer has an elongation at break > 800% and a volume resistivity > 0.6 × 10⁻⁶. 18 Ω·cm, melt flow index of 65~85 g / 10min, transmittance of 85~99% at 380~1100 nm, water vapor transmittance of 2~3.9%, and low-temperature notched impact strength of 50~70 KJ / m at -30℃. 2 The notched impact strength of the cantilever beam is 10~20 KJ / m. 2 The heat distortion temperature is 130~160℃.
2. The elastomer according to claim 1, characterized in that, The elastomer has an elongation at break > 850% and a volume resistivity > 0.78 × 10⁻⁶. 18 Ω·cm, melt flow index of 69~76 g / 10min, transmittance of 380~1100 nm of 89~94%, water vapor transmittance of 2.5~3.1%, and low-temperature notched impact strength of 59~65 KJ / m at -30℃. 2 The notched impact strength of the cantilever beam is 13.7~15.1 KJ / m. 2 The heat distortion temperature is 139~151℃.
3. The method for preparing the hydrogenated bio-based terpene binary random copolymer elastomer according to claim 1 or 2, characterized in that, The method described: (1) A binary random copolymer was prepared by copolymerizing bio-based monoterpenes and bio-based sesquiterpenes; (2) The binary random copolymer is dissolved in a solvent to prepare a copolymer solution, and then hydrogenated using a Ziegler-Natta hydrogenation reaction system or a metallocene hydrogenation reaction system to obtain a hydrogenated bio-based terpene binary random copolymer elastomer.
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 can be abbreviated as AB, where A represents one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, dichlorodiethylaluminum, dichloroethylaluminum, and sesquiethylaluminum chloride, and B represents one or more of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2-tert-butylphenol, and 2,6-di-tert-butyl-4-ethylphenol. The reaction temperature is -50℃ to 70℃, and the reaction time is 10 to 360 min.
7. 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.
8. The method according to claim 7, characterized in that, The specific process of using iron coordination polymerization: Under anhydrous and oxygen-free conditions, iron catalyst, co-catalyst, bio-based monoterpenes and bio-based sesquiterpenes monomers and solvent are added to the reactor, and the polymerization reaction is carried out under stirring at 0~100 °C for 10~120 min.
9. The method according to claim 8, characterized in that, The iron catalyst can be any one of the following structural formulas: 。 10. 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.
11. The method according to claim 3, characterized in that, The Ziegler-Natta hydrogenation reaction process in step (2) is as follows: Under an argon atmosphere, a copolymer solution, a mixture of catalyst and co-catalyst is added to a dry, high-temperature reactor. The gas in the reactor is replaced three times with hydrogen. The reactor speed is adjusted to 200-600 rpm, the hydrogenation reaction pressure is 1-4 MPa, the temperature is raised to 45-70℃, and the reaction is carried out for 1-3 hours.
12. The method according to claim 11, characterized in that, The catalyst is one or more of titanium dioxide, titanium sulfate, titanium hydroxide, nickel naphthenate, nickel bromide, nickel cobaltide, and nickel fluoride. 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 (1~300):1, and the molar ratio of the catalyst to the co-catalyst is 1:(1~10).
13. The method according to claim 12, characterized in that, The catalyst is titanium sulfate or nickel naphthenate, and the co-catalyst is one or more of aluminum acetate, aluminum hydroxide, sesquiethyl aluminum chloride, DMAO, and MMAO.
14. The method according to claim 6, 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.
15. The method according to claim 14, 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 speed was adjusted to 200-800 rpm, the hydrogenation reaction pressure was 2.5-3.0 MPa, the temperature was raised to 50-80℃, and the reaction was carried out for 0.1-1.5 h.
16. The method according to claim 15, characterized in that, The catalyst, bis(titanium) cyclopentadiene, includes bis(titanium) dichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodichlorodimethylaluminum, trimethylaluminum, tri-n-butylaluminum, triisobutylaluminum, triethylaluminum, and diisobutylaluminum hydride. The lithium metal compound is one or more of lithium fluoride, lithium carbonate, lithium phosphate, lithium nitride, lithium hydroxide, and lithium chloride. The mass ratio of the copolymer to the bis(titanium) cyclopentadiene in the copolymer solution is (1~5000):1, the molar ratio of the bis(titanium) cyclopentadiene to the alkylaluminum is 1:(1~6), and the molar ratio of the bis(titanium) cyclopentadiene to the lithium metal compound is 1:(1~8).
17. The hydrogenated bio-based terpene binary random copolymer elastomer according to claim 1 or 2 is used to prepare hot melt adhesives and their membrane products for use in photovoltaic solar energy and batteries, automotive interiors, clothing, footwear, electronics, wall coverings, construction, filtration or pharmaceutical fields.