Bio-based thermoplastic elastomer composition and application thereof in transmission conveyor belt

Abstract

The invention discloses a bio-based thermoplastic elastomer composition and application thereof in a transmission conveyor belt, and belongs to the field of compositions of high-molecular compounds. The bio-based thermoplastic elastomer composition comprises the following raw materials in parts by weight: 30-70 parts of a modified polyurethane elastomer, 15-45 parts of a thermoplastic polyester elastomer, 2-6 parts of a compatilizer, 1-3 parts of an antioxidant and 1-3 parts of a lubricant, the modified polyurethane elastomer is prepared from poly (trimethylene ether glycol), bio-based polyol, 1, 5-pentamethylene diisocyanate, a functional filler and 1, 4-butanediol through a reaction. The bio-based thermoplastic elastomer composition disclosed by the invention not only has good mechanical properties and processability, but also has excellent wear resistance, heat resistance and durability when being used for a transmission conveyor belt.

Description

Technical Field

[0001] This invention belongs to the field of polymer compound compositions, specifically relating to a bio-based thermoplastic elastomer composition and its application in transmission conveyor belts. Background Technology

[0002] Thermoplastic elastomers (TPEs), as a class of polymer materials that combine the physical and mechanical properties of vulcanized rubber with the processing convenience of thermoplastics, do not require thermal vulcanization and can be directly molded through thermoplastic processing techniques such as injection molding, extrusion, and blow molding. This significantly improves production efficiency and simplifies the process, making them widely used in industrial products such as seals, transmission belts, conveyor belts, wires and cables, shock absorbers, and hoses. Currently, mainstream TPE materials on the market mainly rely on petrochemical raw material systems. For example, polyurethane thermoplastic elastomers (TPUs) are prepared by chemical reaction between isocyanates and polyesters or polyether polyols. Although they exhibit outstanding performance in terms of wear resistance and elasticity, they generally suffer from insufficient heat stability, yellowing after long-term use, and high compression set. Especially in heavy-duty industrial scenarios such as mining, building materials, and ports, the cover layer of transmission and conveyor belts needs to withstand continuous and severe friction and scratching from irregular, sharp, and heavy-duty materials. Traditional petroleum-based TPE materials, due to their limited durability, are prone to gradual surface wear and structural failure, thereby shortening their service life and increasing replacement frequency and operating costs.

[0003] To address the depletion of petroleum resources and the pressure of carbon emissions, bio-based thermoplastic elastomers are prepared using biomass raw materials such as vegetable oil-derived polyols (e.g., castor oil-based polyols), aiming to reduce dependence on petrochemical resources and improve sustainability. However, existing bio-based TPE compositions still have significant shortcomings in terms of abrasion resistance, heat stability, and durability, severely limiting their application in high-end industrial products, especially in the field of transmission and conveyor belts, and making it difficult to meet the stringent performance requirements of transmission and conveyor belts under heavy-load, high-friction conditions. For example, Chinese patent CN109438653A discloses a bio-based thermoplastic polyurethane elastomer and its preparation method, comprising the following components: 30-95wt% polyol component (containing 50-100wt% bio-based polyester polyol), 0-25wt% chain extender component (containing 50-100wt% bio-based chain extender), 5-45wt% diisocyanate component (containing 10-60wt% bio-based diisocyanate), and 0.001-0.1wt% catalyst component (containing 50-100wt% non-tin environmentally friendly catalyst). This thermoplastic polyurethane elastomer has the advantages of high bio-based content, good mechanical properties, and fast molding, but its wear resistance and heat resistance stability still need to be improved. Chinese patent CN110229471A discloses a biodegradable thermoplastic elastomer material and its preparation method, comprising the following raw materials in parts by weight: 50-70 parts PBAT resin, 5-25 parts biodegradable polyol ester, 10-20 parts SEBS, and 5-15 parts compatibilizer. The biodegradable polyol ester is selected from at least one of trimethylolpropane oleate, trimethylolpropane octyl decanoate, pentaerythritol oleate, and isooctyl stearate. This thermoplastic elastomer has the advantages of good elasticity and good degradation performance, but its heat resistance and durability still need improvement. Furthermore, existing flame-retardant and antistatic TPEs developed to meet specific safety regulations improve safety performance, but often at the expense of mechanical properties, resulting in insufficient strength and increased production costs, failing to balance the durability and economy of conveyor belts. Therefore, there is an urgent need to develop a new bio-based thermoplastic elastomer composition that, while maintaining environmental friendliness, further improves comprehensive properties such as wear resistance, heat resistance, and durability. Summary of the Invention

[0004] To address the shortcomings of the existing technology, the present invention provides a bio-based thermoplastic elastomer composition. By incorporating modified polyurethane elastomer and thermoplastic polyester elastomer in a synergistic effect, the overall performance of the elastomer composition, such as wear resistance, heat stability, and durability, is further improved.

[0005] The technical solution adopted in this invention is as follows:

[0006] This invention provides a bio-based thermoplastic elastomer composition, comprising the following parts by weight of raw materials:

[0007] 30-70 parts modified polyurethane elastomer, 15-45 parts thermoplastic polyester elastomer, 2-6 parts compatibilizer, 1-3 parts antioxidant, and 1-3 parts lubricant.

[0008] Preferably, the method for preparing the modified polyurethane elastomer is as follows:

[0009] Polytrimethylene ether glycol and bio-based polyol were added to a reactor and heated under nitrogen protection. 1,5-pentanediisocyanate and tin catalyst were added to react and a prepolymer was obtained. Under stirring, functional filler was added to the prepolymer and stirred and mixed. Then 1,4-butanediol was added and stirred and mixed. The mixture was poured into a mold for curing, cooled, and demolded to obtain a modified polyurethane elastomer.

[0010] Preferably, the weight ratio of the polytrimethylene ether glycol, bio-based polyol, 1,5-pentanediisocyanate, functional filler, and 1,4-butanediol is 20-40:15-25:6-10:2-4:2-4.

[0011] Preferably, the tin catalyst is at least one of stannous octoate, dibutyltin dilaurate, and dibutyltin diacetate.

[0012] Preferably, the preparation method of the bio-based polyol is as follows:

[0013] Epoxidized soybean oil, cellulose nanocrystals, hydrogenated rosin, isosorbide, and triethylamine were added to a reaction vessel and heated under nitrogen protection. DMC catalyst and some propylene oxide were added and heated under nitrogen protection. The remaining propylene oxide was added dropwise, and the reaction was continued. After cooling, bio-based polyol was obtained.

[0014] Preferably, the weight ratio of the epoxidized soybean oil, cellulose nanocrystals, hydrogenated rosin, isosorbide, and propylene oxide is 12-18:1-3:2-8:5-10:80-100.

[0015] Preferably, the preparation method of the functional filler is as follows:

[0016] Ti2TaAlC2 MAX phase ceramic material and hydrofluoric acid aqueous solution were added to a reaction vessel, heated under nitrogen protection, filtered, washed with water, and dried to obtain pretreated filler. N-aminoethyl-γ-aminopropyltrimethoxysilane and ethanol aqueous solution were added to a reaction vessel, heated under nitrogen protection, and the above pretreated filler was added to react. Filtered, washed with water, and dried to obtain functional filler.

[0017] Preferably, the weight ratio of the Ti2TaAlC2 MAX phase ceramic material, hydrofluoric acid aqueous solution, and N-aminoethyl-γ-aminopropyltrimethoxysilane is 3-6:50-80:1-3.

[0018] Preferably, the viscosity (25°C) of the polytrimethylene ether glycol is 1600-1900 cps, and the hydroxyl value is 53.4-59.0 mg KOH / g. Polytrimethylene ether glycol is an environmentally friendly bio-based polyol that exhibits good elasticity, flexibility, biodegradability, and processability in polyurethane elastomer applications.

[0019] Preferably, the epoxidized soybean oil has an epoxy value ≥6% and an acid value ≤0.6mgKOH / g.

[0020] Preferably, the cellulose nanocrystals have a diameter of 10-30 nm and a length of 200-500 nm. The cellulose nanocrystals are unmodified cellulose nanocrystals with hydroxyl groups retained on their surface.

[0021] Preferably, the acid value of the hydrogenated rosin is ≥160 mgKOH / g. This hydrogenated rosin has advantages such as good antioxidant properties and high thermal stability.

[0022] Preferably, the Ti2TaAlC2 MAX phase ceramic material has a sheet diameter of 2-15 μm.

[0023] This invention utilizes bio-based raw materials, epoxidized soybean oil, isosorbide, and hydrogenated rosin, to react under specific conditions. This successfully embeds bio-based rigid structural units, such as the rigid bisfuran ring of isosorbide and the stable hydrogenated phenanthrene ring of hydrogenated rosin, along with bio-based nanoscale reinforcing points like cellulose nanocrystals, into a polyol structural network via covalent bonds. This not only significantly improves the cohesive energy, microphase separation, and chain segment mobility barrier of the polyurethane hard segments by increasing hard segments and introducing sterically hindered rigid ring structures, thus significantly raising its thermal decomposition initiation temperature, but also... The hydrophobic aromatic ring structure of rosin also enhances the antioxidant capacity of the chain segments. Meanwhile, cellulose nanocrystals, as nano-reinforcers with high specific surface area and high modulus, have hydroxyl groups on their surface that are incorporated into the structural network through reaction, playing a dual reinforcing role as nano-crosslinking points and rigid filler particles. On the one hand, they strengthen the physical crosslinking network, restrict molecular chain slippage, and provide support for wear resistance. On the other hand, their uniformly dispersed nanoparticles can effectively hinder crack propagation and act as thermally stable barriers to delay heat transfer. Together, they lay the structural foundation for the high heat resistance and high durability of the elastomer.

[0024] Secondly, using Ti2TaAlC2 MAX phase as a precursor, the functional filler is selectively etched into an Al layer to obtain two-dimensional nanosheets with hydroxyl groups on the surface. The active hydroxyl sites on the surface undergo a condensation reaction with Si-OH generated from the hydrolysis of diaminosilane (N-aminoethyl-γ-aminopropyltrimethoxysilane), firmly grafting highly reactive amino groups onto the surface of the nanosheets. When the functional filler participates in polyurethane polymerization, its surface amino groups preferentially react with the isocyanate groups of the prepolymer to form strong urea bonds, thereby allowing the two-dimensional nanosheets to be chemically covalently bonded into the three-dimensional cross-linked network of polyurethane. This strong interfacial bonding... This design ensures efficient stress transfer from the flexible matrix to the high-modulus, high-hardness two-dimensional nanosheets. During friction, the two-dimensional nanosheets, acting as hard bearing points, effectively resist plowing. Their layered structure also provides solid lubrication at the friction interface through relative slippage between the layers, thereby reducing the coefficient of friction and wear rate. Under thermal conditions, their excellent thermal stability and the dense physical barrier network formed in the matrix effectively delay the escape of thermal decomposition products and heat transfer, further increasing the overall thermal decomposition temperature of the elastomer in conjunction with the bio-based rigid unit.

[0025] The modified polyurethane elastomer prepared in this invention and the Hytrel® type thermoplastic polyester elastomer achieve optimized combination of micro-phase states through a reactive compatibilizer (ethylene-methyl acrylate-glycidyl methacrylate random terpolymer). A chemical bridge is formed at the interface between the two phases, which greatly improves compatibility and interfacial adhesion. This allows the hard crystalline segments of the polyester to fully bear the load as a reinforcing phase, and together with the modified polyurethane matrix and functional fillers, they form a stable composite system. This achieves a simultaneous improvement in the heat resistance, wear resistance and durability of the elastomer composition.

[0026] Preferably, the melt index (2.16 kg / 220°C) of the thermoplastic polyester elastomer is 18-21 g / 10 min, and the product type is Hytrel. ® RS 40F3 NC010 (DuPont). The Hytrel ® Type II thermoplastic polyester elastomers combine the flexibility of rubber with the mechanical strength and processability of thermoplastics, making them suitable for injection molding processes. At the same time, they are of renewable origin, containing at least 50% renewable raw materials, and have good strength, toughness, elasticity, impact resistance and other properties.

[0027] Preferably, the method for preparing the modified polyurethane elastomer is as follows:

[0028] By weight, 20-40 parts of polytrimethylene ether glycol and 15-25 parts of bio-based polyol are added to a reactor. Under nitrogen protection, the temperature is raised to 70-80℃, and 6-10 parts of 1,5-pentanediisocyanate and 0.01-0.03 parts of tin catalyst are added and reacted for 2-3 hours to obtain a prepolymer. Under stirring conditions of 70-80℃ and 500-650 rpm, 2-4 parts of functional filler are added to the above prepolymer and stirred for 1-3 minutes. Then, 2-4 parts of 1,4-butanediol are added and stirred for 1-3 minutes. The mixture is poured into a mold for curing, cooled, and demolded to obtain a modified polyurethane elastomer.

[0029] Preferably, the temperature of the mold is 95-105℃ and the curing time is 5-8h.

[0030] Preferably, the preparation method of the bio-based polyol is as follows:

[0031] By weight, 12-18 parts of epoxidized soybean oil, 1-3 parts of cellulose nanocrystals, 2-8 parts of hydrogenated rosin, 5-10 parts of isosorbide, and 0.2-0.5 parts of triethylamine are added to a reactor. Under nitrogen protection, the temperature is raised to 70-80℃ and reacted for 2-4 hours. After the reaction, water and triethylamine are removed. Then, 0.02-0.05 parts of DMC catalyst and 5-15 parts of propylene oxide are added. Under nitrogen protection, the temperature is raised to 105-115℃ and reacted for 20-35 minutes. Then, 75-85 parts of propylene oxide are added dropwise. After the addition is complete, the reaction is carried out for 1-3 hours. After the reaction, residual propylene oxide is removed, and the mixture is cooled to obtain bio-based polyol.

[0032] Preferably, the dripping time is 0.5-1.5 hours.

[0033] Preferably, the preparation method of the functional filler is as follows:

[0034] By weight, 3-6 parts of Ti2TaAlC2 MAX phase ceramic material and 50-80 parts of hydrofluoric acid aqueous solution are added to a reactor. Under nitrogen protection, the temperature is raised to 32-40℃ and reacted for 30-42 hours. After filtration, washing with water and drying, the pretreated filler is obtained. 1-3 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 50-80 parts of ethanol aqueous solution are added to a reactor. Under nitrogen protection, the temperature is raised to 45-55℃, and the above pretreated filler is added and reacted for 5-8 hours. After filtration, washing with water and drying, the functional filler is obtained.

[0035] Preferably, the concentration of the hydrofluoric acid aqueous solution is 25-35 wt%.

[0036] Preferably, the concentration of the ethanol aqueous solution is 80-90 wt%.

[0037] Preferably, the compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate.

[0038] Preferably, the melt index (2.16 kg / 190 °C) of the ethylene-methyl acrylate-glycidyl methacrylate random terpolymer is 9.5-10.5 g / 10 min, and the grafting rate is ≥5%.

[0039] Preferably, the antioxidant is composed of antioxidant 1010 and antioxidant 168; the weight ratio of antioxidant 1010 to antioxidant 168 is 5-10:3.

[0040] Preferably, the lubricant is at least one of calcium stearate, pentaerythritol stearate, oxidized polyethylene wax, ethylene bis-stearamide, and oleamide.

[0041] The present invention also provides a method for preparing a bio-based thermoplastic elastomer composition, comprising the following steps:

[0042] Modified polyurethane elastomer, thermoplastic polyester elastomer, compatibilizer, antioxidant, and lubricant are premixed in a mixer, then added to a twin-screw extruder for melt blending, and extruded and granulated to obtain a bio-based thermoplastic elastomer composition.

[0043] Preferably, the mixing machine rotates at 120-180 rpm and the premixing time is 2-6 min.

[0044] Preferably, the extruder temperature is 180-200℃, the residence time is 90-120s, and the screw speed is 200-250rpm.

[0045] The present invention also provides an application of a bio-based thermoplastic elastomer composition in the preparation of transmission conveyor belts.

[0046] The beneficial effects of this invention are as follows:

[0047] The bio-based thermoplastic elastomer composition prepared by this invention utilizes a modified polyurethane elastomer, prepared by reacting polytrimethylene ether glycol, bio-based polyol, 1,5-pentanediisocyanate, functional filler, and 1,4-butanediol, in synergy with a thermoplastic polyester elastomer. This further improves the wear resistance, heat stability, and durability of the elastomer composition. Transmission conveyor belts prepared with this composition exhibit excellent overall performance and a long service life. This invention also provides a method for preparing the above-mentioned bio-based thermoplastic elastomer composition. Detailed Implementation

[0048] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] The raw materials used in the examples are described below:

[0050] Thermoplastic polyester elastomer, model: Hytrel ® RS 40F3 NC010, Melt Index (2.16kg / 220℃): 20g / 10min, Manufacturer: DuPont, USA.

[0051] Ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, model: EPA-810, melt index (2.16kg / 190℃): 10g / 10min, grafting rate: ≥5%, manufacturer: Hangzhou Haiyi Polymer Materials Co., Ltd.

[0052] Epoxidized soybean oil, CAS: 8013-07-8, epoxy value: ≥6%, acid value: ≤0.6mgKOH / g, manufacturer: Jiangxi Xinhe Chemical Co., Ltd.

[0053] Cellulose nanocrystals, No.: XFJ180, (pure hydroxyl groups, powder), diameter: 10-30nm, length: 200-500nm, manufacturer: Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0054] Hydrogenated rosin, model: Staron3136, acid value: ≥160mgKOH / g, manufacturer: Guangdong Hualin Chemical Co., Ltd.

[0055] N-Aminoethyl-γ-aminopropyltrimethoxysilane, CAS: 1760-24-3, Manufacturer: Shanghai Yi'en Chemical Technology Co., Ltd.

[0056] Bio-based silica, model: EVOSIL® NS175MS, specific surface area: 165±20m² 2 / g, Manufacturer: Anhui Jinhua Silicon Nanomaterials Technology Co., Ltd.

[0057] Enzymatically hydrolyzed lignin, model: LIG-Ⅱ, phenolic hydroxyl content: ≥3%, manufacturer: Shandong Longli Biotechnology Co., Ltd.

[0058] γ-glycidyl etheroxypropyltrimethoxysilane, CAS: 2530-83-8, Manufacturer: Shanghai Yi'en Chemical Technology Co., Ltd.

[0059] DMC catalyst, i.e., bimetallic cyanide catalyst, cobalt ions: 11±1wt%, zinc ions: 23±1wt%, manufacturer: Shanghai Sanmei Chemical Co., Ltd.

[0060] Ti2TaAlC2 MAX phase ceramic material, No.: XFK30, flake diameter: 2-15μm, purity: >90wt%, manufacturer: Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0061] Polytrimethylene ether glycol, model: PO3G H2000, viscosity (25°C): 1600-1900cps, hydroxyl value: 53.4-59.0mgKOH / g, manufacturer: Guangzhou Haoyi New Material Technology Co., Ltd.

[0062] Example 1

[0063] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0064] The composition comprises 60 parts modified polyurethane elastomer, 35 parts thermoplastic polyester elastomer, 5 parts compatibilizer, 1.5 parts antioxidant, and 1.5 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 7:3. The lubricant is calcium stearate.

[0065] The method for preparing the modified polyurethane elastomer is as follows:

[0066] By weight, 15 parts of epoxidized soybean oil, 2 parts of cellulose nanocrystals, 4 parts of hydrogenated rosin, 7 parts of isosorbide, and 0.3 parts of triethylamine were added to a reaction vessel. The mixture was heated to 75°C under nitrogen protection and kept at this temperature for 3 hours. After the reaction, water and triethylamine were removed. Then, 0.03 parts of DMC catalyst and 10 parts of propylene oxide were added. The mixture was heated to 110°C under nitrogen protection and kept at this temperature for 30 minutes. Then, 80 parts of propylene oxide were added dropwise over a period of 1 hour. After the addition was complete, the mixture was kept at this temperature for 2 hours. After the reaction, residual propylene oxide was removed, and the mixture was cooled to room temperature to obtain a bio-based polyol.

[0067] Five parts of Ti2TaAlC2 MAX phase ceramic material and 60 parts of 30wt% hydrofluoric acid aqueous solution were added to a reactor. The mixture was heated to 35℃ under nitrogen protection and kept at this temperature for 36 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the pretreated filler. Two parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 60 parts of 85wt% ethanol aqueous solution were added to a reactor. The mixture was heated to 50℃ under nitrogen protection, and then the above pretreated filler was added and kept at this temperature for 6 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the functional filler.

[0068] 30 parts of polytrimethylene ether glycol and 20 parts of bio-based polyol were added to a reactor and heated to 75°C under nitrogen protection. Then, 8 parts of 1,5-pentanediisocyanate and 0.02 parts of dibutyltin dilaurate were added and the mixture was kept at this temperature for 2.5 hours to obtain a prepolymer. Under the conditions of 75°C and 600 rpm stirring, 3 parts of functional filler were added to the prepolymer and stirred for 3 minutes. Then, 3 parts of 1,4-butanediol were added and stirred for 2 minutes. The mixture was immediately poured into a mold at 100°C and kept at this temperature for 6 hours to cure. After cooling to room temperature, the mixture was demolded to obtain a modified polyurethane elastomer.

[0069] The method for preparing the above-mentioned bio-based thermoplastic elastomer composition includes the following steps:

[0070] Modified polyurethane elastomer, thermoplastic polyester elastomer, compatibilizer, antioxidant, and lubricant were premixed in a mixer for 5 minutes at a speed of 150 rpm. Then, the mixture was added to a twin-screw extruder for melt blending, extrusion, and granulation to obtain a bio-based thermoplastic elastomer composition. The extruder temperatures were: zone 1 185℃, zone 2 190℃, zone 3 195℃, zone 4 200℃, zone 5 200℃, and die head 195℃; the residence time was 100 seconds; and the screw speed was 220 rpm.

[0071] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0072] Example 2

[0073] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0074] The mixture comprises 30 parts modified polyurethane elastomer, 15 parts thermoplastic polyester elastomer, 2 parts compatibilizer, 1 part antioxidant, and 1 part lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 5:3. The lubricant is calcium stearate. The preparation method of the modified polyurethane elastomer is the same as in Example 1.

[0075] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0076] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0077] Example 3

[0078] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0079] The mixture comprises 70 parts modified polyurethane elastomer, 45 parts thermoplastic polyester elastomer, 6 parts compatibilizer, 3 parts antioxidant, and 3 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 10:3. The lubricant is calcium stearate. The preparation method of the modified polyurethane elastomer is the same as in Example 1.

[0080] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0081] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0082] Example 4

[0083] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0084] The composition comprises 60 parts modified polyurethane elastomer, 35 parts thermoplastic polyester elastomer, 5 parts compatibilizer, 1.5 parts antioxidant, and 1.5 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 7:3. The lubricant is calcium stearate.

[0085] The method for preparing the modified polyurethane elastomer is as follows:

[0086] By weight, 5 parts of Ti2TaAlC2 MAX phase ceramic material and 60 parts of 30wt% hydrofluoric acid aqueous solution were added to a reactor. The mixture was heated to 35℃ under nitrogen protection and kept at that temperature for 36 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the pretreated filler. 2 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 60 parts of 85wt% ethanol aqueous solution were added to a reactor. The mixture was heated to 50℃ under nitrogen protection, and then the above pretreated filler was added and kept at that temperature for 6 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the functional filler.

[0087] 50 parts of polytrimethylene ether glycol were added to a reactor and heated to 75°C under nitrogen protection. Then, 8 parts of 1,5-pentanediisocyanate and 0.02 parts of dibutyltin dilaurate were added and reacted at this temperature for 2.5 hours to obtain a prepolymer. Under stirring conditions of 75°C and 600 rpm, 3 parts of functional filler were added to the prepolymer and stirred for 3 minutes. Then, 3 parts of 1,4-butanediol were added and stirred for 2 minutes. The mixture was immediately poured into a mold at 100°C, kept at this temperature for 6 hours to cure, cooled to room temperature, and demolded to obtain a modified polyurethane elastomer.

[0088] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0089] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0090] Example 5

[0091] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0092] The composition comprises 60 parts modified polyurethane elastomer, 35 parts thermoplastic polyester elastomer, 5 parts compatibilizer, 1.5 parts antioxidant, and 1.5 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 7:3. The lubricant is calcium stearate.

[0093] The method for preparing the modified polyurethane elastomer is as follows:

[0094] By weight, 15 parts of epoxidized soybean oil, 2 parts of bio-based silica, 4 parts of hydrogenated rosin, 7 parts of isosorbide, and 0.3 parts of triethylamine were added to a reaction vessel. The mixture was heated to 75°C under nitrogen protection and kept at this temperature for 3 hours. After the reaction, water and triethylamine were removed. Then, 0.03 parts of DMC catalyst and 10 parts of propylene oxide were added. The mixture was heated to 110°C under nitrogen protection and kept at this temperature for 30 minutes. Then, 80 parts of propylene oxide were added dropwise over a period of 1 hour. After the addition was complete, the mixture was kept at this temperature for 2 hours. After the reaction, residual propylene oxide was removed, and the mixture was cooled to room temperature to obtain a bio-based polyol.

[0095] Five parts of Ti2TaAlC2 MAX phase ceramic material and 60 parts of 30wt% hydrofluoric acid aqueous solution were added to a reactor. The mixture was heated to 35℃ under nitrogen protection and kept at this temperature for 36 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the pretreated filler. Two parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 60 parts of 85wt% ethanol aqueous solution were added to a reactor. The mixture was heated to 50℃ under nitrogen protection, and then the above pretreated filler was added and kept at this temperature for 6 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the functional filler.

[0096] 30 parts of polytrimethylene ether glycol and 20 parts of bio-based polyol were added to a reactor and heated to 75°C under nitrogen protection. Then, 8 parts of 1,5-pentanediisocyanate and 0.02 parts of dibutyltin dilaurate were added and the mixture was kept at this temperature for 2.5 hours to obtain a prepolymer. Under the conditions of 75°C and 600 rpm stirring, 3 parts of functional filler were added to the prepolymer and stirred for 3 minutes. Then, 3 parts of 1,4-butanediol were added and stirred for 2 minutes. The mixture was immediately poured into a mold at 100°C and kept at this temperature for 6 hours to cure. After cooling to room temperature, the mixture was demolded to obtain a modified polyurethane elastomer.

[0097] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0098] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0099] Example 6

[0100] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0101] The composition comprises 60 parts modified polyurethane elastomer, 35 parts thermoplastic polyester elastomer, 5 parts compatibilizer, 1.5 parts antioxidant, and 1.5 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 7:3. The lubricant is calcium stearate.

[0102] The method for preparing the modified polyurethane elastomer is as follows:

[0103] By weight, 15 parts of epoxidized soybean oil, 2 parts of cellulose nanocrystals, 4 parts of enzymatically hydrolyzed lignin, 7 parts of isosorbide, and 0.3 parts of triethylamine were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 75°C and maintained for 3 hours. After the reaction, water and triethylamine were removed. Then, 0.03 parts of DMC catalyst and 10 parts of propylene oxide were added. Under nitrogen protection, the temperature was raised to 110°C and maintained for 30 minutes. Then, 80 parts of propylene oxide were added dropwise over 1 hour. After the addition was complete, the reaction was maintained for 2 hours. After the reaction, residual propylene oxide was removed, and the mixture was cooled to room temperature to obtain bio-based polyol.

[0104] Five parts of Ti2TaAlC2 MAX phase ceramic material and 60 parts of 30wt% hydrofluoric acid aqueous solution were added to a reactor. The mixture was heated to 35℃ under nitrogen protection and kept at this temperature for 36 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the pretreated filler. Two parts of N-aminoethyl-γ-aminopropyltrimethoxysilane and 60 parts of 85wt% ethanol aqueous solution were added to a reactor. The mixture was heated to 50℃ under nitrogen protection, and then the above pretreated filler was added and kept at this temperature for 6 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the functional filler.

[0105] 30 parts of polytrimethylene ether glycol and 20 parts of bio-based polyol were added to a reactor and heated to 75°C under nitrogen protection. Then, 8 parts of 1,5-pentanediisocyanate and 0.02 parts of dibutyltin dilaurate were added and the mixture was kept at this temperature for 2.5 hours to obtain a prepolymer. Under the conditions of 75°C and 600 rpm stirring, 3 parts of functional filler were added to the prepolymer and stirred for 3 minutes. Then, 3 parts of 1,4-butanediol were added and stirred for 2 minutes. The mixture was immediately poured into a mold at 100°C and kept at this temperature for 6 hours to cure. After cooling to room temperature, the mixture was demolded to obtain a modified polyurethane elastomer.

[0106] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0107] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0108] Example 7

[0109] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0110] The composition comprises 60 parts modified polyurethane elastomer, 35 parts thermoplastic polyester elastomer, 5 parts compatibilizer, 1.5 parts antioxidant, and 1.5 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 7:3. The lubricant is calcium stearate.

[0111] The method for preparing the modified polyurethane elastomer is as follows:

[0112] By weight, 15 parts of epoxidized soybean oil, 2 parts of cellulose nanocrystals, 4 parts of hydrogenated rosin, 7 parts of isosorbide, and 0.3 parts of triethylamine were added to a reaction vessel. The mixture was heated to 75°C under nitrogen protection and kept at this temperature for 3 hours. After the reaction, water and triethylamine were removed. Then, 0.03 parts of DMC catalyst and 10 parts of propylene oxide were added. The mixture was heated to 110°C under nitrogen protection and kept at this temperature for 30 minutes. Then, 80 parts of propylene oxide were added dropwise over a period of 1 hour. After the addition was complete, the mixture was kept at this temperature for 2 hours. After the reaction, residual propylene oxide was removed, and the mixture was cooled to room temperature to obtain a bio-based polyol.

[0113] 30 parts of polytrimethylene ether glycol and 20 parts of bio-based polyol were added to a reactor and heated to 75°C under nitrogen protection. Then, 8 parts of 1,5-pentanediisocyanate and 0.02 parts of dibutyltin dilaurate were added and the mixture was kept at this temperature for 2.5 h to obtain a prepolymer. Under the conditions of 75°C and 600 rpm stirring, 3 parts of 1,4-butanediol were added to the prepolymer and stirred for 3 min. Then, 3 parts of 1,4-butanediol were added and stirred for 2 min. The mixture was immediately poured into a mold at 100°C and kept at this temperature for 6 h to cure. After cooling to room temperature, the mixture was demolded to obtain a modified polyurethane elastomer.

[0114] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0115] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0116] Example 8

[0117] A bio-based thermoplastic elastomer composition comprising the following parts by weight of raw materials:

[0118] The composition comprises 60 parts modified polyurethane elastomer, 35 parts thermoplastic polyester elastomer, 5 parts compatibilizer, 1.5 parts antioxidant, and 1.5 parts lubricant. The compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate. The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 7:3. The lubricant is calcium stearate.

[0119] The method for preparing the modified polyurethane elastomer is as follows:

[0120] By weight, 15 parts of epoxidized soybean oil, 2 parts of cellulose nanocrystals, 4 parts of hydrogenated rosin, 7 parts of isosorbide, and 0.3 parts of triethylamine were added to a reaction vessel. The mixture was heated to 75°C under nitrogen protection and kept at this temperature for 3 hours. After the reaction, water and triethylamine were removed. Then, 0.03 parts of DMC catalyst and 10 parts of propylene oxide were added. The mixture was heated to 110°C under nitrogen protection and kept at this temperature for 30 minutes. Then, 80 parts of propylene oxide were added dropwise over a period of 1 hour. After the addition was complete, the mixture was kept at this temperature for 2 hours. After the reaction, residual propylene oxide was removed, and the mixture was cooled to room temperature to obtain a bio-based polyol.

[0121] Five parts of Ti2TaAlC2 MAX phase ceramic material and 60 parts of 30wt% hydrofluoric acid aqueous solution were added to a reactor. The mixture was heated to 35℃ under nitrogen protection and kept at this temperature for 36 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the pretreated filler. Two parts of γ-glycidyl etheroxypropyltrimethoxysilane and 60 parts of 85wt% ethanol aqueous solution were added to a reactor. The mixture was heated to 50℃ under nitrogen protection, and then the above pretreated filler was added and kept at this temperature for 6 hours. After the reaction, the mixture was filtered, washed with water, and dried to obtain the functional filler.

[0122] 30 parts of polytrimethylene ether glycol and 20 parts of bio-based polyol were added to a reactor and heated to 75°C under nitrogen protection. Then, 8 parts of 1,5-pentanediisocyanate and 0.02 parts of dibutyltin dilaurate were added and the mixture was kept at this temperature for 2.5 hours to obtain a prepolymer. Under the conditions of 75°C and 600 rpm stirring, 3 parts of functional filler were added to the prepolymer and stirred for 3 minutes. Then, 3 parts of 1,4-butanediol were added and stirred for 2 minutes. The mixture was immediately poured into a mold at 100°C and kept at this temperature for 6 hours to cure. After cooling to room temperature, the mixture was demolded to obtain a modified polyurethane elastomer.

[0123] The preparation method of the bio-based thermoplastic elastomer composition is the same as that in Example 1.

[0124] The bio-based thermoplastic elastomer composition was used to prepare standard specimens on an injection molding machine for performance testing.

[0125] Test Example 1

[0126] The thermal decomposition temperature of each bio-based thermoplastic elastomer composition was determined using a TGA thermogravimetric analyzer to evaluate its thermal stability. Test conditions: The temperature was increased from 25°C to 600°C under a nitrogen atmosphere at a heating rate of 10°C / min, and the temperature at which 5% weight loss occurred was recorded (T0). 5% The results are shown in Table 1.

[0127] Durability was evaluated by conducting thermo-oxidative aging tests on various bio-based thermoplastic elastomer compositions. Test conditions: aged at 120℃ for 36 hours under air conditions. Tensile strength before and after the aging test was determined according to the method in national standard GB / T 528-2009, and the tensile strength reduction rate was calculated. The tensile strength reduction rate % = (value before aging - value after aging) / value before aging × 100%. The results are shown in Table 1.

[0128] The abrasion resistance of each example of bio-based thermoplastic elastomer composition was determined according to the method in national standard GB / T 3960-2016; test conditions: rotation at 200 r / min, test time 2h, load 196N, and the wear rate was calculated; where, the wear rate % = (mass before wear - mass after wear) / mass before wear × 100%; the results are shown in Table 1.

[0129] Table 1 Performance test results of bio-based thermoplastic elastomer compositions

[0130] <![CDATA[T 5% / ℃]]> Tensile strength reduction rate / % Wear rate / % Example 1 345.5 9.62 1.172 Example 2 346.3 8.87 1.143 Example 3 344.6 10.39 1.198 Example 4 305.2 24.26 3.326 Example 5 340.0 14.01 1.853 Example 6 338.8 16.98 2.165 Example 7 317.9 22.45 3.179 Example 8 341.5 13.22 1.693

[0131] A comparison of Examples 1-8 shows that the bio-based thermoplastic elastomer compositions of Examples 1-3 exhibit excellent heat stability, durability, and abrasion resistance. This is because their elastomer composition formulations utilize specific modified polyurethane elastomers and thermoplastic polyester elastomers, which work synergistically to significantly improve the overall performance of the elastomer composition. Compared to Example 1, Examples 4-6 did not use bio-based polyols containing cellulose nanocrystals, hydrogenated rosin, isosorbide, etc., in the preparation of the modified polyurethane elastomers. Examples 7-8 did not use functional fillers in the preparation of the modified polyurethane elastomers. As shown in Table 1, this leads to a decrease in the overall performance of the elastomer compositions, including heat stability, durability, and abrasion resistance. This indicates that the modified polyurethane elastomers prepared using the specific methods described above in the elastomer composition formulations of this invention are crucial for achieving improved overall performance.

[0132] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A bio-based thermoplastic elastomer composition, characterized in that: It includes the following raw materials by weight: 30-70 parts modified polyurethane elastomer, 15-45 parts thermoplastic polyester elastomer, 2-6 parts compatibilizer, 1-3 parts antioxidant, and 1-3 parts lubricant; The method for preparing the modified polyurethane elastomer is as follows: Polytrimethylene ether glycol and bio-based polyol were added to a reactor and heated under nitrogen protection. 1,5-pentanediisocyanate and tin catalyst were added to react and a prepolymer was obtained. Under stirring conditions, functional filler was added to the prepolymer and stirred to mix. Then 1,4-butanediol was added and stirred to mix. The mixture was poured into a mold for curing, cooled, and demolded to obtain the final product.

2. The bio-based thermoplastic elastomer composition according to claim 1, characterized in that: The preparation method of the bio-based polyol is as follows: Epoxidized soybean oil, cellulose nanocrystals, hydrogenated rosin, isosorbide, and triethylamine were added to a reaction vessel and heated under nitrogen protection. DMC catalyst and part of propylene oxide were added and heated under nitrogen protection. The remaining propylene oxide was added dropwise, and the reaction was continued until the mixture was cooled to obtain the final product.

3. The bio-based thermoplastic elastomer composition according to claim 1, characterized in that: The preparation method of the functional filler is as follows: Ti2TaAlC2 MAX phase ceramic material and hydrofluoric acid aqueous solution were added to a reaction vessel, heated under nitrogen protection, filtered, washed with water, and dried to obtain pretreated filler; N-aminoethyl-γ-aminopropyltrimethoxysilane and ethanol aqueous solution were added to a reaction vessel, heated under nitrogen protection, and the above pretreated filler was added to react, filtered, washed with water, and dried to obtain the final product.

4. The bio-based thermoplastic elastomer composition according to claim 1, characterized in that: The tin catalyst is at least one of stannous octoate, dibutyltin dilaurate, and dibutyltin diacetate.

5. The bio-based thermoplastic elastomer composition according to claim 1, characterized in that: The thermoplastic polyester elastomer has a melt index of 18-21 g / 10 min at 2.16 kg and 220 °C; the compatibilizer is a random terpolymer of ethylene-methyl acrylate-glycidyl methacrylate; the antioxidant is composed of antioxidant 1010 and antioxidant 168; the lubricant is at least one of calcium stearate, pentaerythritol stearate, oxidized polyethylene wax, ethylene bis-stearamide, and oleamide.

6. The bio-based thermoplastic elastomer composition according to claim 1, characterized in that: The weight ratio of polytrimethylene ether glycol, bio-based polyol, 1,5-pentanediisocyanate, functional filler, and 1,4-butanediol is 20-40:15-25:6-10:2-4:2-4.

7. The bio-based thermoplastic elastomer composition according to claim 2, characterized in that: The weight ratio of the epoxidized soybean oil, cellulose nanocrystals, hydrogenated rosin, isosorbide, and propylene oxide is 12-18:1-3:2-8:5-10:80-100.

8. The bio-based thermoplastic elastomer composition according to claim 3, characterized in that: The weight ratio of the Ti2TaAlC2MAX phase ceramic material, hydrofluoric acid aqueous solution, and N-aminoethyl-γ-aminopropyltrimethoxysilane is 3-6:50-80:1-3.

9. A method for preparing a bio-based thermoplastic elastomer composition according to any one of claims 1-8, characterized in that: Includes the following steps: Modified polyurethane elastomer, thermoplastic polyester elastomer, compatibilizer, antioxidant, and lubricant are premixed in a mixer, then added to a twin-screw extruder for melt blending, and extruded and granulated to obtain a bio-based thermoplastic elastomer composition.

10. The use of the bio-based thermoplastic elastomer composition according to any one of claims 1-8 in the preparation of transmission conveyor belts.