Furandicarboxylate bio-based cross-linkable elastomer and preparation method thereof

Abstract

The present invention discloses a furandicarboxylate bio-based crosslinkable elastomer and a preparation method thereof. The preparation method comprises: uniformly mixing furandicarboxylate or furandicarboxylate, a linear saturated dibasic acid or linear saturated dibasic acid ester, a linear unsaturated dibasic acid or linear unsaturated dibasic acid ester, and a diol; adding a catalyst and an antioxidant; heating the mixture to above 150°C; gradually heating the mixture under an inert atmosphere; and reacting the mixture at 150-190°C for 3-7 hours to obtain an intermediate product; stirring the intermediate product for a polycondensation reaction at a vacuum degree of 30-400 Pa and a temperature of 200-260°C for 3-8 hours to obtain a crude product; and dissolving, washing, and drying the crude product to obtain a finished product. The polyfurandicarboxylate bio-based elastomer prepared by the present invention has good mechanical properties and processing properties; and the composite material after crosslinking and filler reinforcement can greatly improve tensile strength, good resilience, low permanent deformation, and high tensile strength.

Description

Technical Field

[0001] The present invention relates to the technical field of polyesters, in particular to a furandicarboxylate bio-based cross-linkable elastomer and a preparation method and a reinforcement method thereof. Background Art

[0002] Rubber is a highly elastic polymer material with reversible deformation. It undergoes significant deformation when an external force is applied, but recovers after the force is removed. It exhibits high resilience, strength, and wear resistance. Existing synthetic rubbers include styrene-butadiene rubber, nitrile-butadiene rubber, butadiene rubber, isoprene rubber, ethylene-propylene rubber, and chloroprene rubber. However, the monomers used to synthesize these rubbers are petrochemical products, non-renewable, and generate net carbon emissions. To alleviate the energy crisis and reduce carbon emissions, the development of bio-based polymer materials derived from renewable resources has become a key focus.

[0003] Bio-based polymers are polymer materials synthesized from bio-based raw materials, directly utilized or modified from natural polymers, or produced through microbial metabolism. Currently, bio-based polymers garnering widespread attention include polyethylene furandicarboxylate (PEF), polybutylene furandicarboxylate (PBF), polyhydroxyalkanoates (PHA), polylactic acid (PLA), chitosan, polybutylene succinate (PBS), polycaprolactone (PCL), and polybutylene adipate / terephthalate (PBAT). These polymers are derived from renewable monomers, have low carbon emissions, and some are biodegradable. According to a 2017 report by the European Bioplastics Association, bio-based plastic production accounts for approximately one percent of total annual plastic production (approximately 320 million tons). As demand continues to grow, more bio-based polymers, their applications, and related products are emerging. Global bio-based plastic production was 1.2 million tons in 2012, increasing to approximately 2.05 million tons in 2017. Global bio-based plastic production is projected to reach approximately 2.5 million tons in 2022.

[0004] In 2004, the U.S. Department of Energy selected 12 representative bio-based platform compounds from over 300 bio-based compounds, including 2,5-furandicarboxylic acid, 1,4-butanedioic acid, and itaconic acid. Among these, 2,5-furandicarboxylic acid, with its aromatic structure, garnered significant attention, being hailed as a "sleeping giant" by DuPont and DSM. Bio-based 2,5-furandicarboxylic acid has various preparation pathways depending on the raw material source: 1. Hydroxymethylfurfural is extracted from cellulose, oxidized to furoic acid, and synthesized via a disproportionation reaction under alkaline, high-temperature conditions; 2. Hexaconic acid is used as the raw material for oxidation synthesis, where 2-furoate and a tertiary alcohol are added to a chloroform solution and refluxed at 100°C for 12 hours to obtain 2,5-furandicarboxylic acid. Currently, furan bio-based polyesters are mainly used to prepare bio-based plastics such as PBF, PEF or non-cross-linkable thermoplastic polyester elastomers (TPEE). Furan polyesters have important and extensive uses in industries such as engineering plastics, automobiles, electronics and industrial manufacturing.

[0005] Furandicarboxylate bioplastics, represented by polyethylene furandicarboxylate (PEF), offer comparable performance to petroleum-based polyester plastics such as polyethylene terephthalate (PET), and possess distinct advantages in certain areas. PEF has a lower melting point, which reduces production and processing energy consumption. It also exhibits higher tensile modulus and tensile strength. PEF also offers advantages in barrier properties: the strong polarity and asymmetry of the furan ring in PEF result in oxygen and carbon dioxide permeabilities an order of magnitude lower than those of PET, making it advantageous for packaging applications. More importantly, PEF offers significant environmental advantages. Furthermore, PEF can be recycled, similar to PET, demonstrating its environmental friendliness and sustainable development. Considering PEF's advantages in thermal, mechanical, gas barrier, and environmental performance, it holds broad application prospects. However, as a new bioplastic, it also has performance limitations, such as slow crystallization, low toughness, and low elongation at break. People synthesize high-toughness plastics or elastomeric materials by introducing diols or linear dibasic acids with more carbon atoms. Usually, the relative PEF strength decreases significantly after the toughness is improved.

[0006] Chinese invention patent publication number CN107312167A describes a bio-based thermoplastic elastomer prepared by replacing terephthalic acid with 2,5-furandicarboxylic acid and introducing a flexible aliphatic lactone via a ring-opening reaction. By adjusting the monomer content, various products, ranging from hard plastics to elastomers, can be prepared. Chinese invention patent publication number CN108059715A describes a thermoplastic polyester elastomer prepared by polycondensation using 2,5-furandicarboxylic acid, short-chain branched diols, and hydroxyl-terminated oligomers as the primary raw materials. The resulting polyester elastomer exhibits a breaking strength that does not decrease with increasing soft segment content, a recovery rate of 45-90% at an initial deformation of 200%, and an elongation at break of 300-1300%. The furan-based polyester elastomers reported in these two patents suffer from poor resilience and low tensile strength, and cannot be reinforced or vulcanized, limiting their functionality and applications as elastomers.

[0007] Therefore, it is an urgent problem to prepare a polyester elastomer with high molecular weight, low glass transition temperature, non-crystallization, reinforcement and cross-linking using furandicarboxylic acid or its ester as the main monomer and expand the application of furan-based polyester in the field of elastomers. Summary of the Invention

[0008] To this end, the present invention provides a furandicarboxylate bio-based cross-linkable elastomer with high molecular weight, low glass transition temperature, non-crystallization, reinforcement and cross-linking, and a preparation method of the elastomer.

[0009] Different from the prior art, the above technical solution provides a furandicarboxylate bio-based cross-linkable elastomer, the molecular formula of which is shown in the following formula I:

[0010]

[0011] In formula I, R is one of the following groups: -CH=CH-; m is an integer of 2-5, n is an integer of 2-10; x, y, and z are all integers greater than 1; the furandicarboxylate bio-based cross-linkable elastomer has a number average molecular weight of 30,000 to 75,000 and a glass transition temperature of -65 to -5°C.

[0012] The furandicarboxylate bio-based cross-linkable elastomer of the present invention contains a furan ring in its molecular formula and has a high molecular weight, a number average molecular weight of 30,000 to 75,000, a glass transition temperature range of -65 to -5°C, good resilience and high strength, and has broad application prospects.

[0013] The introduction of a linear diacid structure into the molecular formula of the furandicarboxylate bio-based crosslinkable elastomer lowers the glass transition temperature of polyester and disrupts the regularity of polyester chain segments, making it less likely to crystallize. Furthermore, the furandicarboxylate bio-based crosslinkable elastomer contains crosslinkable double bonds within its molecular chain. This polyester elastomer composite material, prepared by crosslinking with peroxides or other compounds as crosslinking agents and then reinforcing with fillers, exhibits excellent overall performance and promising application prospects.

[0014] The present invention also provides a method for preparing the furandicarboxylate bio-based cross-linkable elastomer, which comprises the following steps:

[0015] 1) Furandicarboxylic acid or furandicarboxylate, a linear saturated dibasic acid or a linear saturated dibasic acid ester, a linear unsaturated dibasic acid or a linear unsaturated dibasic acid ester, and a diol are uniformly mixed, a catalyst and an antioxidant are added, the temperature is raised to above 150° C., and then the temperature is gradually raised under an inert atmosphere. The mixture is reacted at 150-190° C. for 3-7 hours to obtain an intermediate product; the ratio of the total mole number of the three dibasic acids or dibasic acid esters to the mole number of the diol is 1:0.9-1.5;

[0016] 2) The intermediate product is stirred for polycondensation reaction at a vacuum degree of 30-400 Pa and 200-260° C. for 3-8 hours to obtain a crude product, and the crude product is dissolved, washed, and dried to obtain the furandicarboxylate bio-based crosslinkable elastomer.

[0017] In step 1) of the present invention, after the temperature is raised to 150° C., the reaction is carried out by gradually increasing the temperature. The purpose of gradually increasing the temperature is to react the volatile monomers with low reactivity first, and then to make the non-volatile monomers with high reactivity more easily react after the temperature is raised, so that the monomers can react as completely as possible.

[0018] The transesterification reaction in step 1) is terminated when the amount of methanol obtained in the collection flask reaches 95% of the theoretical amount produced. The esterification reaction time is generally 3 to 7 hours. The transesterification temperature is controlled at 150 to 190°C in the present invention. This is because the esterification process is an endothermic reaction. Although excessively high temperatures can further accelerate the transesterification reaction rate, they will also lead to accelerated side reactions. Excessively low temperatures cannot meet the heat requirements of the transesterification reaction and dissolution process.

[0019] In step 2) of the present invention, the reaction temperature is controlled at 200-260° C. This is because too low a temperature prevents the polycondensation reaction from proceeding, while too high a reaction temperature increases side reactions such as thermal degradation during the polycondensation reaction, resulting in a poorer color of the product.

[0020] The polycondensation reaction pressure of step 2) of the present invention is controlled at 30-400Pa. Too high a pressure (i.e., a worse vacuum effect) will result in the inability to achieve the removal of small molecules in the polycondensation reaction and the oxidation of the product. The polycondensation reaction termination phenomenon of the present invention is the occurrence of the Weissenberg effect. The polycondensation reaction stirring speed of the present invention is 50-130rpm. The viscosity of the material in the initial stage of the polycondensation reaction is low and the molecular weight is small. Using 130rpm can increase the reaction rate. As the molecular weight of the product increases, the viscosity of the material rises and the Weissenberg effect occurs. Reducing the speed delays the Weissenberg effect, which can make the material react further and improve the molecular weight of the product. When the speed drops to 50rpm, the Weissenberg effect occurs and the polycondensation reaction ends.

[0021] Preferably, the ratio of the total molar number of the three dibasic acids or dibasic esters to the molar number of the diol is 1:0.95-1.3.

[0022] The present invention utilizes the above-mentioned preparation method. Adding a linear saturated dibasic acid or linear saturated dibasic acid ester during the reaction can lower the glass transition temperature of the polyester and disrupt the regularity of the polyester chain segments, making the polyester less likely to crystallize. Simultaneously, the introduction of a linear unsaturated dibasic acid or linear unsaturated dibasic acid ester into the reaction introduces double bond groups into the molecular chain, providing crosslinking points for the polyester elastomer. Crosslinking with the double bond groups using peroxide or other crosslinking methods is then achieved, and inorganic fillers are then used for reinforcement to produce a polyfuran dicarboxylate bio-based elastomer composite. This polyester elastomer composite exhibits excellent overall performance and promising application prospects.

[0023] The present invention prepares a high-molecular-weight bio-based crosslinkable polyfurandicarboxylic acid elastomer through an ester exchange-polycondensation synthesis method. By adjusting the dosage ratios of various dibasic acids or dibasic esters, and the dosage ratios of dibasic acids or dibasic esters to diols, a polyester elastomer with a glass transition temperature ranging from -65°C to -5°C can be obtained. This bio-based polyester elastomer has an adjustable glass transition temperature and crosslinking point (double bond group content). It can be crosslinked with crosslinking agents such as peroxides, reinforced with common fillers, and processed using traditional rubber processing methods such as open mills. The resulting bio-based crosslinked polyfurandicarboxylic acid elastomer composite exhibits good resilience and high strength, and has broad application prospects.

[0024] Furthermore, if the total molar amount of furandicarboxylic acid or furandicarboxylic acid ester, linear saturated dibasic acid or linear saturated dibasic acid ester, and linear unsaturated dibasic acid or linear unsaturated dibasic acid ester is 100%, the molar content of the furandicarboxylic acid or furandicarboxylic acid ester is 5 to 80%, more preferably 40 to 60%; the molar content of the linear saturated dibasic acid or linear saturated dibasic acid ester is 10 to 85%; and the molar content of the linear unsaturated dibasic acid or linear unsaturated dibasic acid ester is 5 to 20%.

[0025] By controlling the content of linear unsaturated dibasic acids or linear unsaturated dibasic esters to 5-20%, the double bond group content is controlled, ultimately effectively controlling the crosslinking degree, molecular weight, and glass transition temperature of the polyester elastomer. By controlling the content of linear saturated dibasic acids or linear saturated dibasic esters to 10-85%, the glass transition temperature of the polyester elastomer can be effectively lowered, disrupting the regularity of the polyester chain segments and making the polyester less likely to crystallize. By controlling the content of furandicarboxylic acid or furandicarboxylic acid esters to 5-80%, a polyester elastomer with a glass transition temperature below -5°C can be obtained. When the glass transition temperature is below room temperature, the non-crystallizing polymer can exhibit a highly elastic state at room temperature, making it usable as rubber. Therefore, by controlling the content of furandicarboxylic acid or furandicarboxylic acid esters to 5-80%, a polyester product useful as rubber can be obtained.

[0026] Furthermore, the antioxidant comprises one or more of the following: hydroquinone, 4-methoxyphenol, phosphorous acid, phosphoric acid, pyrophosphoric acid, ammonium phosphate, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, diphenyl phosphate, triphenyl phosphate, diphenyl phosphite, and triphenyl phosphite; the added weight of the antioxidant is 0.1 to 0.3 wt % of the weight of the linear unsaturated dibasic acid or linear unsaturated dibasic acid ester. By adding the antioxidant during the reaction, oxidation of the monomers during the reaction is prevented.

[0027] Preferably, the added amount of the antioxidant is 0.15 to 0.2 wt % of the linear unsaturated dibasic acid or linear unsaturated dibasic acid ester.

[0028] Furthermore, the catalyst comprises a mixture of one or more of the following: tetrabutyl titanate, tetraisopropyl titanate, titanium tetrachloride, titanium glycolate, titanium butoxide, tetraethyl titanate, titanium dioxide, tetramethyl titanate, potassium titanate, stannous oxide, stannous octoate, stannous chloride, tin tetrachloride, tri-n-propyltin acetate, stannous lactate, dibutyltin oxide, antimony trioxide, antimony acetate, zinc acetate, antimony glycolate, and germanium dioxide; the added molar amount of the catalyst is 0.05 to 0.3 mol% of the total molar amount of the dibasic acid or dibasic ester. Preferably, the added molar amount of the catalyst is 0.05 to 0.16 mol% of the total molar amount of the dibasic acid or dibasic ester.

[0029] Furthermore, the furandicarboxylic acid or furandicarboxylic acid ester includes one of the following: 2,5-furandicarboxylic acid, dimethyl 2,5-furandicarboxylate, diethyl 2,5-furandicarboxylate, dipropyl 2,5-furandicarboxylate, and dibutyl 2,5-furandicarboxylate. Because furandicarboxylic acid or furandicarboxylic acid esters have a rigid five-membered ring structure, they can improve the mechanical properties and barrier properties of polyester.

[0030] Furthermore, the linear saturated dibasic acid or linear saturated dibasic acid ester includes one of the following: succinic acid, dimethyl succinate, adipic acid, dimethyl adipate, glutaric acid, adipic acid, and pimelic acid.

[0031] Among them, succinic acid is preferred. Succinic acid includes bio-based succinic acid and chemically synthesized succinic acid, with bio-based succinic acid being preferred. Bio-based succinic acid is produced from crops such as corn and sugarcane through anaerobic microbial fermentation at 35-40°C and a pH of 4-6.5. Due to its high productivity, minimal energy loss, and inexpensive raw materials, its production method is cheaper than traditional chemically synthesized succinic acid.

[0032] Furthermore, the linear unsaturated dibasic acid or linear unsaturated dibasic acid ester includes one of the following: itaconic acid, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, maleic acid, dimethyl maleate, and diethyl maleate. The linear unsaturated dibasic acid or linear unsaturated dibasic acid ester is introduced into the present invention to provide an unsaturated double bond for subsequent cross-linking reaction.

[0033] Furthermore, the diol comprises one or more of the following: ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,9-nonanediol, and 1,10-decanediol. Among these, 1,5-pentanediol is preferred. Furthermore, 1,5-pentanediol is particularly preferred. Using 1,5-pentanediol as a raw material can produce a diol polyester elastomer with an odd number of carbon atoms. Due to the even-odd carbon effect, the regularity of the molecular chain can be further disrupted, rendering the furandicarboxylate bio-based crosslinkable elastomer (polyester compound) non-crystallizable.

[0034] Furthermore, the present invention also discloses a furandicarboxylate bio-based crosslinkable elastomer composite material, which is obtained by crosslinking the furandicarboxylate bio-based crosslinkable elastomer with a peroxide crosslinking agent and then reinforcing it with a filler.

[0035] The method for preparing the furandicarboxylate bio-based cross-linkable elastomer composite material specifically comprises the following steps:

[0036] 1) adding the furandicarboxylate bio-based crosslinkable elastomer, a peroxide crosslinking agent, a filler, and a reaction aid into an internal mixer, and mixing them at room temperature to obtain a uniformly mixed rubber compound; the weight of the inorganic filler added is 5-80% of the weight of the polyfurandicarboxylate elastomer; the weight of the crosslinking agent added is 0.01-0.2% of the weight of the polyester;

[0037] 2) placing the rubber mixture into a flat vulcanizer and vulcanizing it at 165° C. to obtain a polyfuran dicarboxylate bio-based elastomer composite material.

[0038] The filler is one of the following: nano-silica, carbon black, graphene, nano-silica, calcium carbonate, clay, etc., with nano-silica being preferred. Because the polyester elastomer contains bio-based 2,5-furandicarboxylate groups, which contain a large number of ester groups, terminal hydroxyl groups, or terminal carboxyl groups, and the surface of nano-silica contains numerous silanol groups, these groups interact with each other through hydrogen bonding, eliminating the need for surface treatment of the polyester elastomer. Furthermore, nano-silica is not dependent on petroleum. The filler input mass is 5-80% of the mass of the polyfurandicarboxylate elastomer, i.e., 5-80 phr.

[0039] The processing aid may be one of stearic acid, zinc oxide, an antioxidant, or magnesium oxide.

[0040] The crosslinking agent can be an oxide crosslinking agent, such as dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), etc. The amount of the crosslinking agent is 0.01-0.2% of the polyester mass, that is, 0.01-0.2 phr, preferably 0.1-0.15 phr.

[0041] The beneficial effects of the present invention are:

[0042] 1. The polyfurandicarboxylate bio-based elastomer described herein contains furan rings and has a high molecular weight. By adjusting the feed ratio of the various monomers, elastomers with glass transition temperatures ranging from -65°C to -5°C and molecular weights ranging from 30,000 to 75,000 can be obtained. Due to the wide adjustable range of glass transition temperature and molecular weight, the elastomer has a wide range of applications and can ensure excellent mechanical and processability. Furthermore, the polyfurandicarboxylate bio-based elastomer described herein contains cross-linkable double bonds within its molecular chains. Cross-linking can be performed using peroxides or other compounds as cross-linking agents, forming a three-dimensional network structure. This structure can then be reinforced with fillers to produce a polyfurandicarboxylate bio-based elastomer composite. The unreinforced polyfurandicarboxylate bio-based elastomer exhibits a tensile strength of 1.2 to 4.8 MPa after cross-linking. After reinforcement, the tensile strength of the reinforced polyfurandicarboxylate bio-based elastomer composite increases to 11 to 22.6 MPa, significantly improving the tensile strength. Furthermore, the resulting composite exhibits excellent resilience, low permanent set, and high tensile strength.

[0043] At the same time, the polyfuran dicarboxylate bio-based elastomer composite material can be obtained by adopting existing rubber processing technology, and the prepared polyester composite material has excellent comprehensive performance and good application prospects.

[0044] 2. The method for preparing the polyfurandicarboxylate bio-based elastomer of the present invention adopts a low alcohol-acid ratio, which, on the one hand, reduces the self-condensation side reaction of the diol, so that the content of by-products in the final polyfurandicarboxylate bio-based elastomer is low and the product color is good. On the other hand, it reduces the alcohol consumption and reduces the cost.

[0045] 3. The preparation method of the polyfurandicarboxylate bio-based elastomer of the present invention adopts a gradual temperature increase method, so that the volatile and highly reactive monomers in the material react first, and after the temperature is increased, the non-volatile and highly reactive monomers react next, so that all monomers react almost completely, reducing material loss and lowering reaction costs. DETAILED DESCRIPTION

[0046] In order to explain the technical content, structural features, achieved objectives and effects of the technical solution in detail, the following is a detailed description in conjunction with specific embodiments.

[0047] Example 1

[0048] 0.05 mol of 2,5-furandicarboxylic acid, 0.85 mol of succinic acid, 0.1 mol of itaconic acid, 1.5 mol of 1,5-pentanediol, 0.3% of the total molar weight of the dibasic acid isopropyl titanate-antimony trioxide, and 0.1% of the unsaturated dibasic acid 4-methoxyphenol were mixed uniformly and added to a 250 ml three-necked flask. The system was first filled with argon to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 150°C for 2 hours, then raised to 170°C for 1 hour, and then raised to 180°C for 1 hour to ensure complete reaction of the monomers. The stirring rate was 160 rpm. After approximately 30 minutes of reaction, the generated water was collected in a collection flask. After anhydrous product is generated, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 220°C for 6 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0049] Example 2

[0050] 0.6 mol of dimethyl 2,5-furandicarboxylate, 0.3 mol of dimethyl succinate, 0.1 mol of dimethyl maleate, 1.3 mol of 1,7-heptanediol, 0.16% of the total molar weight of dibasic esters, and 0.17% of the unsaturated dibasic esters, diphenyl phosphite, were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel air from the flask, followed by a transesterification reaction. The reaction temperature was initially set at 160°C for 1 hour, then raised to 170°C for 1 hour, and then raised to 180°C for 1 hour to ensure complete reaction of the monomers. The stirring rate was 130 rpm. The methanol generated by the reaction was collected in a collection flask after approximately 35 minutes. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 230°C for 6 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0051] Example 3

[0052] 0.8 mol of dibutyl 2,5-furandicarboxylate, 0.1 mol of dimethyl adipate, 0.1 mol of dimethyl itaconate, 0.95 mol of 1,5-pentanediol, 0.2% of the total molar weight of dibasic esters, and 0.3% of the unsaturated dibasic esters, hydroquinone, were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel air from the flask, followed by a transesterification reaction. The reaction temperature was initially set at 165°C for 1 hour, then raised to 175°C for 2 hours, and then raised to 185°C for 4 hours to ensure complete reaction of the monomers. The stirring rate was 160 rpm. Methanol was obtained in a collection flask after approximately 30 minutes of reaction. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 400 Pa and proceed with the polycondensation reaction at 230°C for 8 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0053] Example 4

[0054] 0.6 mol of dimethyl 2,4-furandicarboxylate, 0.3 mol of dimethyl succinate, 0.1 mol of dimethyl itaconate, 0.9 mol of 1,5-pentanediol, 0.16% of the total molar weight of the dibasic esters in zinc acetate, and 0.2% of the unsaturated dibasic ester in 4-methoxyphenol were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 170°C for 1 hour, then raised to 180°C for 1 hour, and then raised to 190°C for 1 hour to ensure complete reaction of the monomers. The stirring rate was 150 rpm. The reaction lasted approximately 30 minutes, and methanol was collected in a collection flask. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 30 Pa and proceed with the polycondensation reaction at 260°C for 3 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0055] Example 5

[0056] 0.25 mol of dimethyl 2,5-furandicarboxylate, 0.65 mol of dimethyl succinate, 0.10 mol of dimethyl itaconate, 1 mol of 1,5-pentanediol, 0.16% of the total molar weight of dibasic esters, and 0.17% of the unsaturated dibasic esters, dimethyl phosphate, were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 160°C for 1 hour, then raised to 170°C for 1 hour, and then raised to 180°C for 1 hour to ensure complete reaction of the monomers. The stirring rate was 130 rpm. The reaction lasted approximately 30 minutes, and methanol was collected in a collection flask. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 220°C for 4 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0057] Example 6

[0058] 0.6 mol of dimethyl 2,5-furandicarboxylate, 0.25 mol of dimethyl succinate, 0.15 mol of dimethyl itaconate, 1 mol of 1,5-pentanediol, 0.05% of the total molar weight of dibasic esters in tetrabutyl titanate, and 0.15% of the unsaturated dibasic esters in phosphorous acid were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 160°C for 1 hour, then raised to 170°C for 1 hour, and then raised to 180°C for 2 hours to ensure complete reaction of the monomers. The stirring rate was 130 rpm. The reaction lasted for approximately 30 minutes, and methanol was collected in a collection flask. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 230°C for 4 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0059] Example 7

[0060] 0.4 mol of dimethyl 2,5-furandicarboxylate, 0.4 mol of dimethyl succinate, 0.2 mol of dimethyl itaconate, 1.1 mol of 1,5-pentanediol, 0.3% of the total molar weight of dibasic esters (tetrabutyl titanate), and 0.17 wt% of the unsaturated dibasic ester (diphenyl phosphate) were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel air from the flask, followed by a transesterification reaction. The reaction temperature was initially set at 160°C for 1 hour, then raised to 170°C for 1 hour, and then raised to 180°C for 1.5 hours to ensure complete reaction of the monomers. The stirring rate was 130 rpm. The methanol generated by the reaction was collected in a collection flask after approximately 30 minutes. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 220°C for 5 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0061] Example 8

[0062] 0.8 mol of dimethyl 2,5-furandicarboxylate, 0.15 mol of dimethyl succinate, 0.05 mol of dimethyl itaconate, 1 mol of 1,5-pentanediol, 0.16% of the total molar weight of dibasic esters, and 0.17% of the unsaturated dibasic esters, 4-methoxyphenol, were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel air from the flask, followed by a transesterification reaction. The reaction was initially conducted at 160°C for 3.5 hours, then raised to 170°C for 1 hour, and then raised to 180°C for 2.5 hours to ensure complete reaction of the monomers. The stirring rate was 130 rpm. Methanol was obtained in a collection flask after approximately 30 minutes of reaction. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 230°C for 6 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0063] Example 9

[0064] 0.05 mol of 2,5-furandicarboxylic acid, 0.85 mol of pimelic acid, 0.1 mol of itaconic acid, 1.5 mol of 1,8-octanediol, 0.3% of the total molar weight of the dibasic acid isopropyl titanate-germanium dioxide, and 0.1% of the unsaturated dibasic acid in triethyl phosphate were mixed and added to a 250 ml three-necked flask. The system was first filled with argon to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 150°C for 2 hours, then raised to 170°C for 1 hour, and then raised to 180°C for 1 hour to ensure complete reaction of the monomers. The stirring rate was 160 rpm. After approximately 30 minutes of reaction, the generated water was collected in a collection flask. After anhydrous water is generated, disconnect the argon gas and connect a vacuum pump to the tail pipe to evacuate the system to a vacuum of approximately 275 Pa. The polycondensation reaction is carried out at a temperature of 220°C for 6 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, indicating the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. The washed product is placed in a vacuum oven at 40°C and dried for 12 hours.

[0065] Comparative Example 1

[0066] 0.9 mol of dimethyl succinate, 0.1 mol of dimethyl itaconate, 1 mol of 1,5-pentanediol, 0.2 mol% of the total dibasic ester of tetrabutyl titanate, and 0.2 wt% of the unsaturated dibasic ester of 4-methoxyphenol were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 150°C for 3.5 hours, then raised to 160°C for 1 hour, and then raised to 170°C for 1 hour to ensure complete reaction of the monomers. The stirring rate was 130 rpm. The methanol generated by the reaction was collected in a collection flask after approximately 30 minutes. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 220°C for 6 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0067] Comparative Example 2

[0068] 0.9 mol of dimethyl 2,5-furandicarboxylate, 0.1 mol of dimethyl itaconate, 1 mol of 1,5-pentanediol, 0.2 mol of stannous oxide (0.2% mol of the total dibasic ester), and 0.25 wt% of 4-methoxyphenol (0.25 wt% of the unsaturated dibasic ester) were mixed uniformly and added to a 250 ml three-necked flask. Argon was first introduced to the system to expel the air from the flask, and then the transesterification reaction was carried out. The reaction temperature was initially set at 170°C for 1 hour, then raised to 180°C for 1 hour, and then raised to 190°C for 3 hours to ensure complete reaction of the monomers. The stirring rate was 130 rpm. The reaction lasted approximately 30 minutes, and methanol was collected in a collection flask. After all methanol is produced, disconnect the argon gas and connect a vacuum pump to the tail pipe. Evacuate the system to a vacuum of approximately 200 Pa and proceed with the polycondensation reaction at 260°C for 5 hours. When the viscosity of the reactants in the flask increases, reduce the speed to 50 rpm / min until the Weissenberg effect appears, marking the end of the reaction. After the product cools, add an appropriate amount of chloroform to dissolve it. Once it is completely dissolved, wash it three times with cold methanol. Dry the washed product in a vacuum oven at 40°C for 12 hours.

[0069] Example 10

[0070] The polyester prepared in Example 4 was added with 0.01 phr DCP and 2.5 phr stearic acid and mixed in a Brabender internal mixer at room temperature for 4 minutes. The mixture was then added to an open mill and rolled over three times to mix evenly. The resulting mix was placed in a vulcanizer and tested for a cure time of 37 minutes at 165°C. The mix was then compression molded in a flatbed vulcanizer based on the obtained cure time. Finally, a 4×75 dumbbell cutter was used to prepare the sample.

[0071] Example 11

[0072] The polyester prepared in Example 2 was added with 0.2 phr DCP and 2.5 phr stearic acid and mixed in a Brabender internal mixer at room temperature for 4 minutes. The mixture was then added to an open mill and rolled over three times to mix evenly. The resulting mix was placed in a vulcanizer and tested for a vulcanization time of 9 minutes at 165°C. The mix was then compression molded in a flatbed vulcanizer based on the obtained vulcanization time. Finally, a 4×75 dumbbell cutter was used to prepare the sample.

[0073] Example 12

[0074] The polyester prepared in Example 5 was added with 0.15 phr DCP, 2.5 phr stearic acid, and 40 phr nano-silica, and mixed in a Brabender internal mixer at room temperature for 10 minutes. The mixture was then added to an open mill and rolled over three times to mix evenly. The resulting rubber mix was placed in a vulcanizer and tested for a vulcanization time of 10 minutes at 165°C. The resulting vulcanization time was then placed in a flat plate vulcanizer for compression molding. Finally, a 4×75 dumbbell cutter was used to prepare the sample.

[0075] Example 13

[0076] The polyester prepared in Example 6 was added with 0.03 phr DCP, 2.5 phr stearic acid, and 60 phr nano-silica, and mixed in a Brabender internal mixer at room temperature for 4 minutes. The mixture was then added to an open mixer and rolled over three times to mix evenly. The resulting mix was placed in a vulcanizer and tested for a positive vulcanization time of 20 minutes at 165°C. The mix was then placed in a flatbed vulcanizer for compression molding based on the obtained vulcanization time. Finally, a 4×75 dumbbell cutter was used to prepare the sample.

[0077] Example 14

[0078] The polyester prepared in Example 7 was added with 0.15 phr DCP, 2.5 phr stearic acid, and 5 phr nano-silica, and mixed in a Brabender internal mixer at room temperature for 6 minutes. The mixture was then added to an open mill and rolled over three times to mix evenly. The resulting mix was placed in a vulcanizer and tested for a vulcanization time of 7 minutes at 165°C. Based on the obtained vulcanization time, the mix was then placed in a flatbed vulcanizer for compression molding. Finally, a 4×75 dumbbell cutter was used to prepare the sample.

[0079] Example 15

[0080] The polyester prepared in Example 8 was added with 0.2 phr DCP, 2.5 phr stearic acid, and 80 phr nano-silica, and mixed in a Brabender internal mixer at room temperature for 4 minutes. The mixture was then added to an open mixer and rolled over three times to mix evenly. The resulting mix was placed in a vulcanizer and tested for a cure time of 13 minutes at 165°C. Based on the obtained cure time, the mix was then placed in a flatbed vulcanizer for compression molding. Finally, a 4×75 dumbbell cutter was used to prepare the sample.

[0081] Examples 1-9 above each prepared polyfurandicarboxylate bio-based elastomers. Comparative Example 1 involved adding only a linear saturated dibasic acid ester, a linear unsaturated dibasic acid ester, and a diol to react to obtain a polyester compound. Comparative Example 2 involved adding only a furandicarboxylate, a linear unsaturated dibasic acid ester, and a diol to react to obtain a polyester compound. Examples 10-15 each involved further processing the prepared polyfurandicarboxylate bio-based elastomers to obtain polyfurandicarboxylate bio-based elastomer composites.

[0082] The polyfurandicarboxylate bio-based elastomers prepared in Examples 1-9 and Comparative Examples 1-2 were subjected to molecular weight testing, glass transition temperature testing, and observation of crystallization and melting point. Specific test and observation results are shown in Table 1. The specific test methods are as follows:

[0083] Molecular weight determination: Polyester was dissolved in chromatography-grade chloroform and the molecular weight and molecular weight distribution were determined by gel permeation chromatography. Prior to testing, the column was calibrated with PS, the flushing solvent was chromatography-grade chloroform, the solvent flow rate was 1 mL / min, and the polyester concentration was 0.2 g / mL. Molecular weight and molecular weight distribution were determined.

[0084] Glass transition temperature and melting point detection: The procedure for testing polyester is as follows: first, cool the sample from room temperature to 0°C, place the sample in a furnace, and then cool the temperature to -75°C at a rate of 10°C / min and keep it warm for 3 minutes. This is the first cycle; then, heat it from -75°C to 100°C at a rate of 10°C / min and keep it warm for 3 minutes. This is the second cycle. Then, cool it from 100°C to -75°C at a rate of 10°C / min and keep it warm for 3 minutes. This is the second cycle. The test atmosphere is nitrogen.

[0085] Crystallization test: The crystallization state of polyester was tested by X-ray diffraction. Cu Kα was used as the incident wavelength (λ = 0.154nm) and the scanning angle range was 10° to 80°. The test sample size was 20×20×1mm. 3 .

[0086] Table 1 Testing and observation results of polyfurandicarboxylate bio-based elastomer

[0087]

[0088]

[0089] As shown in Table 1, by adjusting the dosage of various monomers, Examples 1-9 can control the molecular weight of the prepared polyfuran dicarboxylate bio-based elastomers to be between 30,000 and 75,000, with a glass transition temperature between -65°C and -5°C, without crystallization. Due to the high molecular weight, low glass transition temperature, and lack of crystallization, the prepared polyfuran dicarboxylate bio-based elastomers can be used as soft, highly elastic rubber matrix materials.

[0090] In Comparative Example 1, since only linear saturated dibasic acid esters and linear unsaturated dibasic acid esters were added to react with diols to obtain the polyester compound, and no furandicarboxylic acid or furandicarboxylic acid ester components were added, the prepared polyester compound had a low glass transition temperature of -53°C, but it crystallized and had a melting point of 37°C. When only linear saturated dibasic acid esters and linear unsaturated dibasic acid esters were polymerized with diols, the prepared polyester compound had a flexible molecular chain and a low glass transition temperature. Linear saturated dibasic acid esters have high regularity, strong intermolecular interactions, and are easy to crystallize. The polyester product prepared after crystallization cannot be used as an elastomer, greatly limiting its scope of application.

[0091] In Comparative Example 2, only furandicarboxylate, linear unsaturated dibasic acid, and diol were added to react to form the polyester compound, without the addition of a linear saturated dibasic acid or linear saturated dibasic acid ester. Consequently, the glass transition temperature of the prepared polyester compound was significantly increased, reaching 7°C. Due to the strong rigidity of the furan rings in the molecular chain added in Example 2 and the absence of flexible linear saturated dibasic acid or linear saturated dibasic acid ester, the glass transition temperature of the prepared polyester compound was high, which in turn reduced the elasticity of the polyester compound and limited its temperature range for use as an elastomer.

[0092] In Examples 10-15, the prepared polyfurandicarboxylate bio-based elastomer was directly cross-linked with peroxide and then processed into a composite material. In Examples 12-15, the prepared polyfurandicarboxylate bio-based elastomer was cross-linked with peroxide, reinforced with fillers, and then processed into a composite material. The prepared composite materials were then tested for tensile strength, elongation at break, tensile stress at break, and permanent set. The test data are shown in Table 2. The specific testing methods are as follows:

[0093] The mechanical properties of polyester and its composites were tested by INSTRON 68TM-10 tensile testing machine with a tensile rate of 500 mm / min and a sample size of 4 × 75 × 1 mm. 3 For each sample, take the average of five tests. Break the original 25mm length (marked as L1) and measure the length of the marked section L2 3 minutes after breaking. Permanent deformation = [(L2 - L1) / L1] × 100%.

[0094] As can be seen from the test data in Table 2, in Example 10, because the mass of peroxide added for the crosslinking reaction was only 0.01% of the mass of the added polyfurandicarboxylate bio-based elastomer, the composite material prepared had a tensile strength of only 1.2 MPa, a modulus of 0.3 MPa at 100% deformation, an elongation at break of 700%, and a permanent set of 6%. Due to the low content of crosslinker, the crosslink density was low, and no filler was added for reinforcement, resulting in low tensile strength, high elongation at break, and large permanent set for the prepared polyfurandicarboxylate bio-based elastomer (polyester compound) composite material.

[0095] In Example 11, the amount of peroxide added to the crosslinking reaction was increased to 0.2% of the mass of the polyfurandicarboxylate bio-based elastomer. The resulting crosslinked composite material had a tensile strength of 4.8 MPa and a modulus of 2.1 MPa at 100% deformation, both improvements compared to Example 10. The elongation at break reached 350%, also improving. Although Example 11 increased the crosslinker content, the lack of filler reinforcement resulted in improved mechanical properties compared to Example 10. However, the overall tensile strength was relatively low and the elongation at break was high, limiting its applicability.

[0096] In Examples 12-15, the prepared polyfuran dicarboxylate bio-based elastomer is cross-linked with peroxide and then reinforced with fillers before being processed into a composite material. The tensile strength of the composite material prepared in this way is increased to above 11.0 MPa, and can reach a maximum of 22.6 MPa. The tensile strength at 100% deformation is increased to above 3.1 MPa, and can reach a maximum of 6.7 MPa. The elongation at break is reduced to a minimum of 257%, and basically no permanent deformation occurs, which greatly expands the scope of application.

[0097] The test data from Examples 12-15 demonstrate that the polyester composites reinforced with fillers prepared in the present invention can be vulcanized and crosslinked at high temperatures. The crosslinked rubber exhibits high tensile strength, low permanent deformation, and high elongation at break. The reinforced bio-based elastomer composites exhibit significantly improved mechanical properties compared to unreinforced polyester materials. The performance of the furandicarboxylate bio-based elastomers prepared in the present invention and their reinforced composites is comparable to that of petroleum-based rubber materials, demonstrating promising application prospects.

[0098] Table 2 Performance test of cross-linked furandicarboxylate bio-based elastomer and its composite materials

[0099]

[0100] It should be noted that, in this document, relational terms such as first and second, etc., are used solely to distinguish one entity or operation from another, and do not necessarily require or imply any actual relationship or order between these entities or operations. Furthermore, the terms "include," "comprise," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or terminal device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or terminal device. Without further limitation, elements defined by the phrase "include..." or "comprising..." do not exclude the presence of additional elements in the process, method, article, or terminal device comprising the elements. Furthermore, in this document, "greater than," "less than," "exceeding," etc., are understood to exclude the number itself; "above," "below," "within," etc., are understood to include the number itself.

[0101] It should be noted that although the above embodiments have been described herein, this does not limit the scope of patent protection of the present invention. Therefore, based on the innovative concept of the present invention, changes and modifications to the embodiments described herein, or equivalent structural or equivalent process transformations made using the contents of the present invention specification, and direct or indirect application of the above technical solutions to other related technical fields are all included in the scope of patent protection of the present invention.

Claims

1. A furandicarboxylate bio-based crosslinkable elastomer, characterized in that: The molecular formula of the furandicarboxylate bio-based cross-linkable elastomer is shown in the following formula I: In formula I, R is one of the following groups: m is an integer of 2-5, n is an integer of 2-10; x, y, and z are all integers greater than 1; the furandicarboxylate bio-based cross-linkable elastomer has a number average molecular weight of 30,000 to 75,000, a glass transition temperature of -65 to -5°C, is non-crystallizable, and can be reinforced.

2. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 1, characterized in that: It includes the following steps: 1) Furandicarboxylic acid or furandicarboxylate, a linear saturated dibasic acid or a linear saturated dibasic acid ester, a linear unsaturated dibasic acid or a linear unsaturated dibasic acid ester, and a diol are uniformly mixed, a catalyst and an antioxidant are added, the temperature is raised to above 150° C., and then the temperature is gradually raised under an inert atmosphere. The mixture is reacted at 150-190° C. for 3-7 hours to obtain an intermediate product; the ratio of the total mole number of the three dibasic acids or dibasic acid esters to the mole number of the diol is 1:0.9-1.5; 2) stirring the intermediate product for polycondensation reaction at a vacuum degree of 30-400 Pa and 200-260° C. for 3-8 hours to obtain a crude product, and dissolving, washing, and drying the crude product to obtain the furandicarboxylate bio-based crosslinkable elastomer; If the total molar amount of furandicarboxylic acid or furandicarboxylic acid ester, linear saturated dibasic acid or linear saturated dibasic acid ester, and linear unsaturated dibasic acid or linear unsaturated dibasic acid ester is 100%, the molar content of furandicarboxylic acid or furandicarboxylic acid ester is 5 to 80%; the molar content of the linear saturated dibasic acid or linear saturated dibasic acid ester is 10 to 85%; and the molar content of the linear unsaturated dibasic acid or linear unsaturated dibasic acid ester is 5 to 20%.

3. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 2, characterized in that: The antioxidant comprises one or a mixture of more than one of the following: hydroquinone, 4-methoxyphenol, phosphorous acid, phosphoric acid, pyrophosphoric acid, ammonium phosphate, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, diphenyl phosphate, triphenyl phosphate, diphenyl phosphite, and triphenyl phosphite; the added mass of the antioxidant is 0.1 to 0.3 wt% of the mass of the linear unsaturated dibasic acid or linear unsaturated dibasic acid ester.

4. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 2, characterized in that: The catalyst comprises one or more of the following: tetrabutyl titanate, tetraisopropyl titanate, titanium tetrachloride, titanium glycolate, titanium butoxide, tetraethyl titanate, titanium dioxide, tetramethyl titanate, potassium titanate, stannous oxide, stannous octoate, stannous chloride, tin tetrachloride, tri-n-propyltin acetate, stannous lactate, dibutyltin oxide, antimony trioxide, antimony acetate, zinc acetate, antimony glycolate, and germanium dioxide; the added molar number of the catalyst is 0.05-0.3 mol% of the total molar number of the dibasic acid or dibasic ester.

5. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 2, characterized in that: The furandicarboxylic acid or furandicarboxylic acid ester includes one or a mixture of more than one of the following: 2,5-furandicarboxylic acid, dimethyl 2,5-furandicarboxylate, diethyl 2,5-furandicarboxylate, dipropyl 2,5-furandicarboxylate, and dibutyl 2,5-furandicarboxylate.

6. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 2, characterized in that: The linear saturated dibasic acid or linear saturated dibasic acid ester includes one of the following: succinic acid, dimethyl succinate, adipic acid, dimethyl adipate, glutaric acid, adipic acid, and pimelic acid.

7. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 2, characterized in that: The linear unsaturated dibasic acid or linear unsaturated dibasic acid ester includes one of the following: itaconic acid, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, maleic acid, dimethyl maleate, and diethyl maleate.

8. The method for preparing a furandicarboxylate bio-based crosslinkable elastomer according to claim 2, characterized in that: The diol includes one or a mixture of more than one of the following: ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,9-nonanediol, and 1,10-decanediol.

9. A furandicarboxylate bio-based cross-linkable elastomer composite material, characterized in that: The furandicarboxylate bio-based crosslinkable elastomer prepared according to any one of claims 2 to 8 is crosslinked with a peroxide crosslinking agent and then reinforced with a filler to obtain the furandicarboxylate bio-based crosslinkable elastomer composite material.

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