Sustainably degradable biological resin based on natural vegetable oil modification and preparation process thereof

Abstract

The invention relates to the technical field of biological resin, in particular to sustainable degradable biological resin based on natural vegetable oil modification and a preparation process of the sustainable degradable biological resin. Comprising the following raw materials in parts by weight: 30 to 60 parts of modified corn oil, 5 to 15 parts of a cross-linking agent, 0.5 to 3 parts of benzoyl peroxide, 5 to 15 parts of triethyl citrate, 10 to 30 parts of regenerated cellulose fiber, 0.5 to 2 parts of 2-hydroxy-4-n-octyloxybenzophenone and 0.5 to 2 parts of triphenyl phosphate. The N-butylpyridine tetrafluoroborate promotes double bond isomerization reaction and changes the positions or types of double bonds in fatty acid chains, so that a more stable molecular structure is generated, connection between molecular chains is tighter due to the stability of the structure, stress is effectively transmitted, and the tensile strength is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of bioresins, in particular to sustainable degradable bioresins modified based on natural vegetable oils and a preparation process thereof. Background Art

[0002] With the increasing severity of global environmental problems such as plastic pollution, resource depletion and climate change, the demand for sustainable materials has become particularly urgent; traditional petroleum-based plastics are gradually restricted in use due to their non-degradability and environmental pollution problems; therefore, the development of biodegradable materials derived from renewable resources has become a research hotspot; natural vegetable oils (such as corn oil, soybean oil, etc.) have attracted widespread attention due to their abundant sources, good biodegradability and low environmental impact; vegetable oils are mainly composed of triglycerides and contain a large number of double bonds, which can be introduced into new functional groups through chemical modification to prepare polymer materials with specific properties.

[0003] However, bio-resins based on vegetable oils often have problems with insufficient tensile strength, hardness and toughness, making it difficult to meet the requirements for material mechanical properties in practical applications. They are prone to deformation and breakage when subjected to external forces. In view of this, we propose a sustainable and degradable bio-resin modified with natural vegetable oil and its preparation process. Summary of the invention

[0004] The purpose of the present invention is to provide a sustainable and degradable bio-resin modified based on natural vegetable oil and a preparation process thereof, so as to solve the problem mentioned in the above background technology that the bio-resin based on vegetable oil often has insufficient tensile strength, hardness and toughness, is difficult to meet the requirements of material mechanical properties in practical applications, and is prone to deformation and fracture when subjected to external force.

[0005] To achieve the above object, the present invention provides a sustainable biodegradable bio-resin modified based on natural plant oil, comprising the following raw materials: 30-60 parts by weight of modified corn oil, 5-15 parts by weight of a cross-linking agent, 0.5-3 parts by weight of benzoyl peroxide, 5-15 parts by weight of triethyl citrate, 10-30 parts by weight of regenerated cellulose fiber, 0.5-2 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5-2 parts by weight of triphenyl phosphite; The modified corn oil is prepared by a double bond isomerization reaction of corn oil and N-butylpyridinium tetrafluoroborate and then adding dimethyl fumarate.

[0006] Preferably, the preparation process of the modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 90-100 parts by weight of corn oil, 1-5 parts by weight of N-butylpyridinium tetrafluoroborate, 30-50 parts by weight of toluene, 5-15 parts by weight of activated alumina, 10-30 parts by weight of dimethyl fumarate, 0.1-0.5 parts by weight of hydroquinone and 0.1-1 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate are stirred at room temperature at a speed of 100-150rpm for 10-20min, toluene is added, and the temperature is slowly raised to 80-120°C, and the reaction is stirred at a speed of 300-600rpm for 2-6h; after the reaction is completed, the reaction system is cooled to room temperature, activated alumina is added, and the reaction is stirred at a speed of 200-300rpm for 15-30min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture is allowed to stand for 10-20min, and filtered to obtain isomerized corn oil; In the reaction system of N-butylpyridinium tetrafluoroborate and corn oil, it acts as an excellent solvent and can well dissolve fatty acids and other components in corn oil, allowing the reactants to fully contact and improve the uniformity and efficiency of the reaction; under the action of N-butylpyridinium tetrafluoroborate, the double bonds on the fatty acid chains in the corn oil undergo an isomerization reaction, the electron cloud distribution around the double bonds will change due to the influence of the ionic liquid, the mobility of the π electron cloud of the double bonds increases, and the double bonds can migrate more easily, thereby causing the position of the double bonds to change, moving from the original position to a more stable or more reaction-friendly position, thereby achieving the isomerization of the double bonds.

[0007] When isomerized corn oil is used to prepare bio-resins and other materials, the change in the position of double bonds can make the bio-resins form a more ideal cross-linked network structure, which helps to improve the mechanical properties of the bio-resins, such as tensile strength, hardness and toughness, and can also improve thermal stability, making the materials more stable at higher temperatures and less prone to deformation or degradation. In addition, isomerized corn oil may have a positive effect on the processing properties of the materials, such as reducing the melt viscosity, making the materials easier to flow and form during processing. After changing the position of double bonds, the structure of corn oil molecules changes, which to a certain extent improves its ability to resist external environmental factors (such as light, oxidation, etc.). When applied to materials, it helps to improve the weather resistance of the materials and extend the service life of the materials. For example, the double bonds of unsaturated fatty acids are prone to self-oxidation reactions during the oxidation process, but through double bond isomerization, a more stable conjugated system can be generated, thereby improving the corrosion resistance and electrical insulation properties of the materials.

[0008] S1.3, add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone and benzoyl peroxide, stir at room temperature at a speed of 100-150rpm for 15-30min, heat the reaction system to 120-160℃ at a speed of 2-3℃ / min, stir and react at a speed of 300-600rpm for 3-8h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; The Diels-Alder reaction is a classic [4+2] cycloaddition reaction. In the reaction, the conjugated diene provides four π electrons, while the dienophile provides two π electrons. New σ bonds and π bonds are formed through the electron rearrangement mechanism, and finally a stable six-membered ring compound is generated. As a dienophile, dimethyl fumarate has good dienophile properties and can effectively react with the conjugated diene to form a stable ring structure. Through the Diels-Alder reaction, new functional groups such as ester groups can be introduced into corn oil molecules. These functional groups can not only improve the physical and chemical properties of the material, but also provide the possibility for further functionalization.

[0009] After isomerization, the double bonds of isomerized corn oil react with dimethyl fumarate to form a denser cross-linked network, making the structure of the bio-resin more stable, thereby significantly improving its mechanical properties, such as tensile strength, tear strength and hardness, making it more able to withstand external forces in practical applications and less prone to damage; the formation of the cross-linked network limits the movement of the molecular chains, making it more difficult for the bio-resin to slide and deform when heated; therefore, the product after the reaction has higher thermal stability and can maintain its shape and performance at higher temperatures, broadening its application range in high temperature environments, which enables it to maintain good performance and extend its service life in humid environments or in application scenarios in contact with water; the reaction may affect the crystallization behavior of the bio-resin and reduce its crystallinity. A lower crystallinity helps to improve the flexibility and transparency of the bio-resin, and also makes it easier to perform thermoplastic molding during processing, and can be more easily processed into products of various shapes and sizes to meet the needs of different application fields.

[0010] S1.4. After the reaction is completed, the reaction product is cooled to room temperature and washed with water to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation to remove water and low-boiling impurities to obtain modified corn oil.

[0011] Preferably, in S1.2, the rate of slowly increasing the temperature is 1-3°C / minute.

[0012] Preferably, in S1.2, the particle size of the activated alumina is 1-3 mm.

[0013] Preferably, in S1.4, the specific steps of washing with water are as follows: the reaction product cooled to room temperature is transferred to a separatory funnel, deionized water is added, and stirred with a magnetic stirrer at 100-300 rpm for 10-20 min; after stirring, the separatory funnel is allowed to stand to separate the aqueous phase, and the process is repeated 3-5 times.

[0014] Preferably, in S1.4, the pressure of the reduced pressure distillation is 10-50 mbar, the distillation temperature is 60-80°C, and the distillation time is 1-3 h.

[0015] On the other hand, the present invention provides a preparation process of a sustainable biodegradable bioresin modified by natural vegetable oil, which is used to prepare the above-mentioned sustainable biodegradable bioresin modified by natural vegetable oil, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 30-60 parts by weight of modified corn oil, 5-15 parts by weight of a crosslinking agent, 0.5-3 parts by weight of benzoyl peroxide, 5-15 parts by weight of triethyl citrate, 10-30 parts by weight of regenerated cellulose fiber, 0.5-2 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5-2 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at a speed of 100-150rpm for 10-15min; slowly add triethyl citrate dropwise, continue stirring at a speed of 100-150rpm for 15-30min, so that the triethyl citrate is evenly dispersed in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 80-120°C, increase the stirring speed to 300-600rpm, and continue stirring for 2-6h to fully polymerize the modified corn oil; after the polymerization reaction, lower the temperature of the reactor to 60-80°C, add a crosslinking agent, and stir at a speed of 200-300rpm for 3-8h; The active groups in the modified corn oil react with the cross-linking agent to form a three-dimensional cross-linked network structure between the molecular chains through chemical bonding, which significantly enhances the intermolecular forces of the bio-resin, thereby improving the material's mechanical properties such as tensile strength, tear strength and hardness, making it better able to withstand external pressure and tension and less prone to breakage; the cross-linked network limits the thermal motion of the molecular chains, making it more difficult for the bio-resin molecular chains to slide and deform when heated, so the material can withstand higher temperatures without softening, deforming or decomposing, expanding its application range in high-temperature environments. For example, it can be used to manufacture some parts that need to withstand a certain high temperature.

[0016] S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 400-800 rpm, and stir for 30-60 min to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 400-800 rpm for 15-30 min to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding; after molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0017] Preferably, in S2.2, the rate of slowly adding triethyl citrate is 0.05-0.1 parts by weight per minute.

[0018] Preferably, in S2.3, the cross-linking agent is polyisocyanate or hexamethylene diisocyanate.

[0019] Preferably, in S2.5, the hot pressing pressure is 5-10 MPa, the hot pressing temperature is 80-120° C., and the hot pressing time is 10-30 min.

[0020] Compared with the prior art, the present invention has the following beneficial effects: 1. In the sustainable biodegradable bioresin modified based on natural vegetable oil and its preparation process, N-butylpyridinium tetrafluoroborate is added because it can promote double bond isomerization reaction and change the position or type of double bonds in fatty acid chains, thereby generating a more stable molecular structure. When the resin is stretched, this structure can make the molecular chains more closely connected, effectively transfer stress, and significantly improve the tensile strength. In addition, N-butylpyridinium tetrafluoroborate also adjusts the flexibility of the molecular chain. While ensuring the strength, the molecular chain absorbs energy through deformation when subjected to force impact, which greatly improves the toughness of the resin and makes it less prone to brittle cracking.

[0021] 2. Dimethyl fumarate is added to the sustainable biodegradable bioresin modified based on natural vegetable oil and its preparation process. When reacting with isomerized corn oil, it can form abundant covalent bonds and construct a tight and stable cross-linked network. This cross-linked network not only significantly improves the tensile strength of the resin, but also effectively disperses stress, thereby enhancing its mechanical properties. At the same time, the stable cross-linked structure can effectively resist the rearrangement and slippage of the molecular chains caused by external forces, significantly improve the fatigue resistance of the resin, and extend its service life under repeated stress environments. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] The present invention provides a sustainable biodegradable bio-resin modified based on natural plant oil, comprising the following raw materials: 30-60 parts by weight of modified corn oil, 5-15 parts by weight of a cross-linking agent, 0.5-3 parts by weight of benzoyl peroxide, 5-15 parts by weight of triethyl citrate, 10-30 parts by weight of regenerated cellulose fiber, 0.5-2 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5-2 parts by weight of triphenyl phosphite; The modified corn oil is prepared by a double bond isomerization reaction of corn oil and N-butylpyridinium tetrafluoroborate and then adding dimethyl fumarate.

[0024] The crosslinking agent is polyisocyanate or hexamethylene diisocyanate, preferably polyisocyanate.

[0025] Example 1: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 30 parts by weight of modified corn oil, 5 parts by weight of polyisocyanate, 0.5 parts by weight of benzoyl peroxide, 5 parts by weight of triethyl citrate, 10 parts by weight of regenerated cellulose fiber, 0.5 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0026] Wherein, the preparation process of modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 3 parts by weight of N-butylpyridinium tetrafluoroborate, 30 parts by weight of toluene, 5 parts by weight of activated alumina, 10 parts by weight of dimethyl fumarate, 0.1 parts by weight of hydroquinone and 0.1 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0027] Example 2: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 45 parts by weight of modified corn oil, 5 parts by weight of polyisocyanate, 0.5 parts by weight of benzoyl peroxide, 5 parts by weight of triethyl citrate, 10 parts by weight of regenerated cellulose fiber, 0.5 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0028] Wherein, the preparation process of modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 3 parts by weight of N-butylpyridinium tetrafluoroborate, 30 parts by weight of toluene, 5 parts by weight of activated alumina, 10 parts by weight of dimethyl fumarate, 0.1 parts by weight of hydroquinone and 0.1 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0029] Example 3: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 60 parts by weight of modified corn oil, 5 parts by weight of polyisocyanate, 0.5 parts by weight of benzoyl peroxide, 5 parts by weight of triethyl citrate, 10 parts by weight of regenerated cellulose fiber, 0.5 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0030] Wherein, the preparation process of modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 3 parts by weight of N-butylpyridinium tetrafluoroborate, 30 parts by weight of toluene, 5 parts by weight of activated alumina, 10 parts by weight of dimethyl fumarate, 0.1 parts by weight of hydroquinone and 0.1 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0031] Example 4: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 60 parts by weight of modified corn oil, 10 parts by weight of polyisocyanate, 1.75 parts by weight of benzoyl peroxide, 10 parts by weight of triethyl citrate, 20 parts by weight of regenerated cellulose fiber, 1.25 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 1.25 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours;

[0032] S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0033] Wherein, the preparation process of modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 1.5 parts by weight of N-butylpyridinium tetrafluoroborate, 40 parts by weight of toluene, 10 parts by weight of activated alumina, 20 parts by weight of dimethyl fumarate, 0.3 parts by weight of hydroquinone and 0.5 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0034] Example 5: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 60 parts by weight of modified corn oil, 10 parts by weight of polyisocyanate, 1.75 parts by weight of benzoyl peroxide, 10 parts by weight of triethyl citrate, 20 parts by weight of regenerated cellulose fiber, 1.25 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 1.25 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0035] Wherein, the preparation process of modified corn oil is as follows: S1.1, weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 2.5 parts by weight of N-butylpyridinium tetrafluoroborate, 40 parts by weight of toluene, 10 parts by weight of activated alumina, 20 parts by weight of dimethyl fumarate, 0.3 parts by weight of hydroquinone and 0.5 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0036] Example 6: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 60 parts by weight of modified corn oil, 10 parts by weight of polyisocyanate, 1.75 parts by weight of benzoyl peroxide, 10 parts by weight of triethyl citrate, 20 parts by weight of regenerated cellulose fiber, 1.25 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 1.25 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0037] Wherein, the preparation process of modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 3.5 parts by weight of N-butylpyridinium tetrafluoroborate, 40 parts by weight of toluene, 10 parts by weight of activated alumina, 20 parts by weight of dimethyl fumarate, 0.3 parts by weight of hydroquinone and 0.5 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0038] Example 7: Sustainable biodegradable bioresin modified by natural vegetable oil and its preparation process, comprising the following steps: S2.1. Weigh the following raw materials in parts by weight respectively: 60 parts by weight of modified corn oil, 10 parts by weight of polyisocyanate, 1.75 parts by weight of benzoyl peroxide, 10 parts by weight of triethyl citrate, 20 parts by weight of regenerated cellulose fiber, 1.25 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 1.25 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at 150 rpm for 15 min; add triethyl citrate dropwise at a rate of 0.1 parts by weight per minute, and continue stirring at 150 rpm for 30 min to evenly disperse the triethyl citrate in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 120°C, increase the stirring speed to 500 rpm, and continue stirring for 6 hours to allow the modified corn oil to fully polymerize; after the polymerization reaction, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 500 rpm for 30 minutes to obtain a mixture; S2.5. Pour the mixture into a preheated mold and perform hot pressing molding at a pressure of 10 MPa, a temperature of 120°C, and a time of 30 minutes. After molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

[0039] Wherein, the preparation process of modified corn oil is as follows: S1.1. Weigh the following raw materials in parts by weight respectively: 95 parts by weight of corn oil, 5 parts by weight of N-butylpyridinium tetrafluoroborate, 40 parts by weight of toluene, 10 parts by weight of activated alumina, 20 parts by weight of dimethyl fumarate, 0.3 parts by weight of hydroquinone and 0.5 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate were stirred at room temperature at a speed of 150 rpm for 20 min, toluene was added, and the temperature was raised to 120°C at a rate of 2°C / min, and the reaction was stirred at a speed of 400 rpm for 6 h; after the reaction, the reaction system was cooled to room temperature, activated alumina with a particle size of 2 mm was added, and the mixture was stirred at a speed of 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil; S1.3, adding isomerized corn oil to a reaction vessel, adding dimethyl fumarate, hydroquinone and benzoyl peroxide, stirring at room temperature at a speed of 150 rpm for 30 min, heating the reaction system to 160°C at a speed of 3°C / min, stirring at a speed of 500 rpm for 8 h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.4. After the reaction is completed, the reaction product is cooled to room temperature, transferred to a separatory funnel, deionized water is added, and stirred at 300 rpm with a magnetic stirrer for 20 minutes; after the stirring is completed, the separatory funnel is allowed to stand, the aqueous phase is separated, and this is repeated 5 times to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation at a pressure of 40 mbar and a temperature of 60°C for 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0040] Comparative Example 1

[0041] The method of Example 6 was adopted, but modified corn oil was not used. Corn oil was directly used to prepare the sustainable degradable bio-resin modified based on natural vegetable oil.

[0042] Comparative Example 2

[0043] The method of Example 6 is used to remove dimethyl fumarate in the preparation process of modified corn oil.

[0044] Comparative Example 3

[0045] The method of Example 6 was adopted, and the modified corn oil was replaced by grape seed oil.

[0046] The present invention prepares a sustainable biodegradable bio-resin based on natural vegetable oil modification by modified corn oil, wherein the performance index inspection items and inspection standards of the sustainable biodegradable bio-resin based on natural vegetable oil modification are as follows:

[0047] According to the national standard GB / T 1040.2, the sample is clamped between the upper and lower clamps of the testing machine, and an appropriate preload is applied to ensure that the sample remains straight and does not deform. The testing machine stretches the sample at a speed of 50mm / min to 500mm / min until the sample breaks; the testing machine automatically records the force applied during the stretching process and the elongation of the sample, draws a stress-strain curve, and calculates the tensile strength and elongation at break through the formula; a higher tensile strength indicates that the material has a strong tensile resistance and can remain intact without breaking under a large external force; a higher elongation at break indicates that the material is not easy to break suddenly when subjected to force and can undergo a large deformation before breaking.

[0048] According to the national standard GB / T 9341, the specimens are placed symmetrically on the supporting device of the testing machine, and a bending load is applied at a speed of 2mm / min to 50mm / min through the loading head located in the middle of the specimen until the specimen breaks or reaches the predetermined maximum deflection; the testing machine will automatically record the load and deflection changes of the specimen during the loading process, draw the stress-strain curve, and extract the bending strength through formula calculation; the bending strength is the ability of a material to resist damage under the action of bending stress. A higher bending strength indicates that the material has a stronger bending resistance and is not prone to yielding or breaking.

[0049] According to the above standards, the sustainable biodegradable bio-resins based on natural plant oil modification prepared in the above Examples 1-7 and Comparative Examples 1-3 were tested, and the obtained data are shown in Table 1:

[0050] Table 1 Performance data of bio-resins of Examples 1-7 and Comparative Examples 1-3

[0051] It can be seen from Examples 4-7 that: when the mass ratio of N-butylpyridinium tetrafluoroborate to corn oil in the modified corn oil gradually increases, the tensile strength, elongation at break and flexural strength of the bioresin gradually increase, but when the mass ratio of N-butylpyridinium tetrafluoroborate to corn oil reaches a certain value, the tensile strength, elongation at break and flexural strength of the bioresin gradually decrease. It can be seen that with the increase of the mass ratio of N-butylpyridinium tetrafluoroborate, the tensile strength, elongation at break and flexural strength of the bioresin are improved, but excessive increase may reduce the tensile strength, elongation at break and flexural strength of the bioresin; N-butylpyridinium tetrafluoroborate is a highly efficient catalyst. As the mass ratio of N-butylpyridinium tetrafluoroborate to corn oil increases, it can more fully catalyze reactions such as double bond isomerization in corn oil, allowing the reaction to proceed more completely and generating more reactive intermediates. These intermediates provide more active sites for subsequent cross-linking reactions, helping to form a more complete cross-linking network, which can more evenly disperse stress and avoid stress concentration, thereby effectively improving the tensile strength and flexural strength of bioresins. N-butylpyridinium tetrafluoroborate may, to a certain extent, induce the corn oil molecular chains to be arranged more regularly during the reaction. When the mass ratio increases, the induction effect is more obvious, which enhances the interaction between the molecular chains and increases the binding force between the molecules. When subjected to external force, the molecular chains can cooperate to resist the external force, thereby improving the tensile strength, bending strength and elongation at break; increasing the mass ratio of N-butylpyridinium tetrafluoroborate appropriately can help improve the solubility between corn oil and other additives, making the entire system more uniform and stable. Good solubility can reduce phase separation and avoid weak areas, so that the material can transfer stress more evenly when subjected to force, thereby improving mechanical properties such as tensile strength, bending strength and elongation at break.

[0052] Further, by comparing Examples 1-3, it can be seen that when other components remain unchanged, only when the proportion of modified corn oil gradually increases, the tensile strength, elongation at break and bending strength of the bio-resin gradually increase. It can be seen that the molecular chain of modified corn oil usually has a certain flexibility. When its proportion increases, the flexibility of the overall molecular chain of the bio-resin will be enhanced. When stretched by external force, the molecular chain can be more easily oriented and slipped, thereby improving the elongation at break; at the same time, the flexibility of the molecular chain also helps to absorb and disperse impact energy, so that the material is not easy to break when bent, and the bending strength is improved; as the proportion of modified corn oil increases, it can be inserted between the molecular chains of the bio-resin, reducing the interaction force between the molecular chains, and making the movement of the molecular chains freer, which is not only conducive to improving the elongation at break, but also to a certain extent. Improve the flexibility of the material, so that the bio-resin can better adapt to deformation when bending, and improve the bending strength; in addition, the modified corn oil has better compatibility and interfacial bonding force with other components in the bio-resin, and can form more physical or chemical bonding points between these components, which can effectively transfer stress to the entire material system, and improve the tensile strength, elongation at break and bending strength of the material.

[0053] By comparing Example 6 with Comparative Example 1, it can be seen that when corn oil is directly used to prepare the sustainable degradable bio-resin modified based on natural vegetable oil without using modified corn oil, the tensile strength, elongation at break and flexural strength of the bio-resin are significantly reduced.

[0054] Taking Example 6 as the optimal example and combining it with Comparative Example 2, it can be seen that in the preparation process of modified corn oil, when dimethyl fumarate is removed, the tensile strength, elongation at break and flexural strength of the bio-resin are significantly reduced; Dimethyl fumarate contains active groups such as double bonds, which can react with functional groups such as hydroxyl groups in corn oil to promote the formation of a cross-linked network, increase the number of cross-linking points, and increase the cross-linking density, thereby enhancing the hardness and wear resistance of the resin; however, after removing dimethyl fumarate, the number of cross-linking points is greatly reduced, the cross-linking density is reduced, and the tensile strength, bending strength and elongation at break of the bio-resin are significantly reduced; this is because the imperfection of the cross-linking network makes it easier for relative slippage between molecular chains to occur. When subjected to tensile force, the molecular chains cannot work together well to resist external forces, and the material is destroyed prematurely; dimethyl fumarate has a certain plasticizing effect and can be inserted between the corn oil molecular chains, making the molecular chains move more freely and increasing the flexibility and plasticity of the material; after removing dimethyl fumarate, the rigidity of the molecular chain is relatively increased, making it difficult for the material to deform when subjected to external forces, and the ability to resist stretching and bending is reduced, thereby resulting in a significant reduction in tensile strength, elongation at break and bending strength.

[0055] Taking Example 6 as the optimal example and combining it with Comparative Example 3, it can be seen that when grape seed oil replaces modified corn oil, the tensile strength, elongation at break and flexural strength of the bio-resin are significantly reduced; The unsaturated fatty acids in grape seed oil are mainly linoleic acid and oleic acid. These fatty acids contain multiple double bonds with different position distributions. These double bonds play a key role in the cross-linking reaction of bio-resins, but the double bond distribution and number of grape seed oil may not be as ideal as those of modified corn oil, resulting in an imperfect network structure formed in the cross-linking reaction; in addition, the content of saturated fatty acids in grape seed oil is relatively low, usually not exceeding 12%, and an appropriate amount of saturated fatty acids helps to improve the regularity and crystallinity of the molecular chain, thereby enhancing the mechanical properties of the material; the triglyceride structure of modified corn oil is more conducive to interacting with other components after modification to form a stable three-dimensional network structure, while the triglyceride structure of grape seed oil cannot provide the same effective support and connection effect when participating in the formation of bio-resins, resulting in poor mechanical properties of bio-resins.

[0056] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions are only preferred examples of the present invention and are not intended to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. Sustainable biodegradable bioresin modified from natural vegetable oil, characterized in that: The invention comprises the following raw materials: 30-60 parts by weight of modified corn oil, 5-15 parts by weight of a cross-linking agent, 0.5-3 parts by weight of benzoyl peroxide, 5-15 parts by weight of triethyl citrate, 10-30 parts by weight of regenerated cellulose fiber, 0.5-2 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5-2 parts by weight of triphenyl phosphite; The modified corn oil is prepared by a double bond isomerization reaction of corn oil and N-butylpyridinium tetrafluoroborate and then adding dimethyl fumarate.

2. The sustainable biodegradable bioresin modified by natural vegetable oil according to claim 1, characterized in that: The preparation process of the modified corn oil is as follows: S1.

1. Weigh the following raw materials in parts by weight respectively: 90-100 parts by weight of corn oil, 1-5 parts by weight of N-butylpyridinium tetrafluoroborate, 30-50 parts by weight of toluene, 5-15 parts by weight of activated alumina, 10-30 parts by weight of dimethyl fumarate, 0.1-0.5 parts by weight of hydroquinone and 0.1-1 parts by weight of benzoyl peroxide; S1.2, corn oil and N-butylpyridinium tetrafluoroborate are stirred at room temperature at a speed of 100-150rpm for 10-20min, toluene is added, and the temperature is slowly raised to 80-120°C, and the reaction is stirred at a speed of 300-600rpm for 2-6h; after the reaction is completed, the reaction system is cooled to room temperature, activated alumina is added, and the reaction is stirred at a speed of 200-300rpm for 15-30min to remove the N-butylpyridinium tetrafluoroborate catalyst, and the mixture is allowed to stand for 10-20min, and filtered to obtain isomerized corn oil; S1.3, add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone and benzoyl peroxide, stir at room temperature at a speed of 100-150rpm for 15-30min, heat the reaction system to 120-160℃ at a speed of 2-3℃ / min, stir and react at a speed of 300-600rpm for 3-8h, so that the isomerized corn oil and dimethyl fumarate are fully reacted; S1.

4. After the reaction is completed, the reaction product is cooled to room temperature and washed with water to remove impurities that may remain in the reaction and unreacted dimethyl fumarate; the reaction product after washing is subjected to reduced pressure distillation to remove water and low-boiling impurities to obtain modified corn oil.

3. The sustainable biodegradable bioresin modified by natural vegetable oil according to claim 2, characterized in that: In the S1.2, the temperature is slowly increased at a rate of 1-3°C per minute.

4. The sustainable biodegradable bioresin modified by natural vegetable oil according to claim 2, characterized in that: In the S1.2, the particle size of the activated alumina is 1-3 mm.

5. The sustainable biodegradable bioresin modified by natural vegetable oil according to claim 2, characterized in that: In S1.4, the specific steps of water washing are as follows: transfer the reaction product cooled to room temperature to a separatory funnel, add deionized water, and stir with a magnetic stirrer at 100-300 rpm for 10-20 min; after stirring, let the separatory funnel stand to separate the aqueous phase, and repeat 3-5 times.

6. The sustainable biodegradable bioresin modified by natural vegetable oil according to claim 2, characterized in that: In S1.4, the pressure of the reduced pressure distillation is 10-50 mbar, the distillation temperature is 60-80° C., and the distillation time is 1-3 h.

7. A process for preparing a sustainable biodegradable bioresin modified by natural vegetable oil, for preparing the sustainable biodegradable bioresin modified by natural vegetable oil as claimed in any one of claims 1 to 6, characterized in that: The preparation process of the sustainable degradable bio-resin modified by natural vegetable oil is as follows: S2.

1. Weigh the following raw materials in parts by weight respectively: 30-60 parts by weight of modified corn oil, 5-15 parts by weight of a crosslinking agent, 0.5-3 parts by weight of benzoyl peroxide, 5-15 parts by weight of triethyl citrate, 10-30 parts by weight of regenerated cellulose fiber, 0.5-2 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone, and 0.5-2 parts by weight of triphenyl phosphite; S2.2, add the modified corn oil into the reactor, stir at a speed of 100-150rpm for 10-15min; slowly add triethyl citrate dropwise, continue stirring at a speed of 100-150rpm for 15-30min, so that the triethyl citrate is evenly dispersed in the modified corn oil; S2.3, add benzoyl peroxide to the reactor, raise the temperature to 80-120°C, increase the stirring speed to 300-600rpm, and continue stirring for 2-6h to fully polymerize the modified corn oil; after the polymerization reaction, lower the temperature of the reactor to 60-80°C, add a cross-linking agent, and stir at a speed of 200-300rpm for 3-8h; S2.4, after the cross-linking reaction is completed, add the regenerated cellulose fiber into the reactor, increase the stirring speed to 400-800 rpm, and stir for 30-60 min to evenly disperse the regenerated cellulose fiber; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue to stir at a speed of 400-800 rpm for 15-30 min to obtain a mixture; S2.

5. Pour the mixture into a preheated mold and perform hot pressing molding; after molding, cool the mold to room temperature to obtain a sustainable and degradable bio-resin modified based on natural vegetable oil.

8. The process for preparing the sustainable biodegradable bioresin modified by natural vegetable oil according to claim 7, characterized in that: In the step S2.2, triethyl citrate is slowly added dropwise at a rate of 0.05-0.1 parts by weight per minute.

9. The process for preparing the sustainable biodegradable bioresin modified by natural vegetable oil according to claim 7, characterized in that: In the above S2.3, the cross-linking agent is polyisocyanate or hexamethylene diisocyanate.

10. The process for preparing the sustainable biodegradable bioresin modified by natural vegetable oil according to claim 7, characterized in that: In the above S2.5, the hot pressing pressure is 5-10 MPa, the hot pressing temperature is 80-120° C., and the hot pressing time is 10-30 min.

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