Sustainable biodegradable bioresin modified with natural vegetable oil and its preparation process

Abstract

The present invention relates to the technical field of bioresins, and more specifically, to a sustainable biodegradable bioresin modified with natural plant oils and a preparation process thereof. The bioresin 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. N-butylpyridinium tetrafluoroborate promotes double bond isomerization reaction, changing the position or type of double bonds in fatty acid chains, thereby generating a more stable molecular structure. The stability of this structure allows for tighter connections between molecular chains, effectively transferring stress and significantly improving tensile strength.

Description

Technical Field

[0001] The present invention relates to the technical field of bioresins, in particular to a sustainable degradable bioresin modified based on natural vegetable oil 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. These double bonds can be introduced into new functional groups through chemical modification to prepare polymer materials with specific properties.

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

[0004] The purpose of the present invention is to provide a sustainably degradable bio-resin modified with natural plant oil and a preparation process thereof, so as to solve the problems mentioned in the above background technology that plant oil-based bio-resins often have insufficient tensile strength, hardness and toughness, making it difficult to meet the requirements for mechanical properties of materials in practical applications and easily deforming and breaking when subjected to external forces.

[0005] To achieve the above objectives, the present invention provides a sustainable biodegradable bioresin 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;

[0006] The modified corn oil is prepared by a double bond isomerization reaction between corn oil and N-butylpyridinium tetrafluoroborate and then adding dimethyl fumarate.

[0007] Preferably, the preparation process of the modified corn oil is as follows:

[0008] S1.1. Weigh the following raw materials in parts by weight: 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;

[0009] S1.2. Stir corn oil and N-butylpyridinium tetrafluoroborate at room temperature at 100-150 rpm for 10-20 minutes, add toluene, and slowly raise the temperature to 80-120°C. Stir and react at 300-600 rpm for 2-6 hours. After the reaction, cool the reaction system to room temperature, add activated alumina, and stir at 200-300 rpm for 15-30 minutes to remove the N-butylpyridinium tetrafluoroborate catalyst. Let stand for 10-20 minutes, and filter to obtain isomerized corn oil.

[0010] In the reaction system with corn oil, N-butylpyridinium tetrafluoroborate acts as an excellent solvent, effectively dissolving fatty acids and other components in the corn oil, allowing the reactants to fully contact and improving 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, and the electron cloud distribution around the double bonds changes under the influence of the ionic liquid. The mobility of the double bond's π electron cloud increases, allowing the double bond to migrate more easily, thereby causing the double bond position to change, moving from its original position to a more stable or more reaction-favorable position, thereby achieving isomerization of the double bond.

[0011] When isomerized corn oil is used to prepare bio-resins and other materials, the change in the position of double bonds can enable the bio-resins to 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 material 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 performance of the material, such as reducing the melt viscosity, making the material easier to flow and form during processing. After changing the position of the double bonds, the structure of the corn oil molecules changes, which to a certain extent improves its ability to resist external environmental factors (such as light, oxidation, etc.); when it is applied to materials, it helps to improve the weather resistance of the material and extend the service life of the material. 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 material.

[0012] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at room temperature at 100-150 rpm for 15-30 minutes. Raise the temperature of the reaction system to 120-160°C at a rate of 2-3°C / minute and stir at 300-600 rpm for 3-8 hours to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0013] The Diels-Alder reaction is a classic [4+2] cycloaddition reaction in which a conjugated diene donates four π electrons, while a dienophile donates two π electrons. Through electron rearrangement, new σ and π bonds are formed, ultimately yielding a stable six-membered ring compound. Dimethyl fumarate, as a dienophile, possesses excellent dienophilic properties and can effectively react with conjugated dienes to form a stable cyclic structure. Through the Diels-Alder reaction, new functional groups, such as ester groups, can be introduced into corn oil molecules. These functional groups not only improve the physical and chemical properties of the material but also provide opportunities for further functionalization.

[0014] 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 bioresin 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 bioresin 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 bioresin and reduce its crystallinity. The lower crystallinity helps to improve the flexibility and transparency of the bioresin, and also makes it easier to thermoform during processing, and can be more easily processed into products of various shapes and sizes to meet the needs of different application fields.

[0015] 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 moisture and low-boiling point impurities to obtain modified corn oil.

[0016] Preferably, in S1.2, the rate of slowly increasing the temperature is 1-3°C / minute.

[0017] Preferably, in S1.2, the particle size of the activated alumina is 1-3 mm.

[0018] 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 the mixture is stirred at 100-300 rpm with a magnetic stirrer for 10-20 minutes; after stirring, the separatory funnel is allowed to stand to separate the aqueous phase, and the process is repeated 3-5 times.

[0019] 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.

[0020] On the other hand, the present invention provides a process for preparing a sustainable biodegradable bioresin modified with natural vegetable oil, which is used to prepare the above-mentioned sustainable biodegradable bioresin modified with natural vegetable oil, comprising the following steps:

[0021] S2.1. Weigh the following raw materials in parts by weight: 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;

[0022] S2.2. Add the modified corn oil to the reactor and stir at 100-150 rpm for 10-15 minutes; slowly add triethyl citrate dropwise and continue stirring at 100-150 rpm for 15-30 minutes to evenly disperse the triethyl citrate in the modified corn oil;

[0023] S2.3. Add benzoyl peroxide to the reactor, raise the temperature to 80-120°C, increase the stirring speed to 300-600 rpm, and continue stirring for 2-6 hours to allow the modified corn oil to fully polymerize. After the polymerization reaction is completed, lower the temperature of the reactor to 60-80°C, add the crosslinking agent, and stir at 200-300 rpm for 3-8 hours.

[0024] The active groups in the modified corn oil react with the cross-linking agent, forming 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 more 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, deformation or decomposition, 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.

[0025] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 400-800 rpm, and stir for 30-60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 400-800 rpm for 15-30 minutes to obtain a mixture;

[0026] 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 biodegradable bioresin modified with natural plant oil.

[0027] Preferably, in S2.2, the rate of slowly adding triethyl citrate dropwise is 0.05-0.1 parts by weight per minute.

[0028] Preferably, in S2.3, the cross-linking agent is polyisocyanate or hexamethylene diisocyanate.

[0029] 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.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. This sustainable, biodegradable bioresin modified with natural plant oil and its preparation process incorporates N-butylpyridinium tetrafluoroborate. This addition promotes double-bond isomerization reactions, changing the position or type of double bonds in fatty acid chains, thereby generating a more stable molecular structure. This structure, when stretched, allows for tighter connections between molecular chains, effectively transferring stress and significantly improving tensile strength. Furthermore, N-butylpyridinium tetrafluoroborate regulates the flexibility of the molecular chains, ensuring strength while allowing them to absorb energy through deformation when subjected to force, significantly improving the toughness of the resin and making it less susceptible to brittle cracking.

[0032] 2. Dimethyl fumarate is added to the sustainable biodegradable bioresin modified with natural vegetable oil and its preparation process. When reacting with isomerized corn oil, it can form abundant covalent bonds, building 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 improving the fatigue resistance of the resin and extending its service life under repeated stress environments. DETAILED DESCRIPTION

[0033] 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 embodiments described 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 making creative efforts are within the scope of protection of the present invention.

[0034] The present invention provides a sustainable biodegradable bioresin 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 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;

[0035] The modified corn oil is prepared by a double bond isomerization reaction between corn oil and N-butylpyridinium tetrafluoroborate and then adding dimethyl fumarate.

[0036] The cross-linking agent is polyisocyanate or hexamethylene diisocyanate, preferably polyisocyanate.

[0037] Example 1: Sustainable biodegradable bioresin modified with natural plant oil and its preparation process, comprising the following steps:

[0038] S2.1. Weigh the following raw materials in parts by weight: 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;

[0039] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0040] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0041] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0042] 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 biodegradable bioresin modified with natural vegetable oil.

[0043] Wherein, the preparation process of modified corn oil is as follows:

[0044] S1.1. Weigh the following raw materials in parts by weight: 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 part by weight of hydroquinone, and 0.1 part by weight of benzoyl peroxide;

[0045] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0046] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0047] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0048] Example 2: Sustainable biodegradable bioresin modified with natural plant oil and its preparation process, comprising the following steps:

[0049] S2.1. Weigh the following raw materials in parts by weight: 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;

[0050] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0051] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0052] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0053] 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 biodegradable bioresin modified with natural vegetable oil.

[0054] Wherein, the preparation process of modified corn oil is as follows:

[0055] S1.1. Weigh the following raw materials in parts by weight: 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 part by weight of hydroquinone, and 0.1 part by weight of benzoyl peroxide;

[0056] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0057] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0058] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0059] Example 3: Sustainable biodegradable bioresin modified with natural plant oil and its preparation process, comprising the following steps:

[0060] S2.1. Weigh the following raw materials in parts by weight: 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;

[0061] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0062] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0063] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0064] 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 biodegradable bioresin modified with natural vegetable oil.

[0065] Wherein, the preparation process of modified corn oil is as follows:

[0066] S1.1. Weigh the following raw materials in parts by weight: 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 part by weight of hydroquinone, and 0.1 part by weight of benzoyl peroxide;

[0067] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0068] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0069] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0070] Example 4: Sustainable biodegradable bioresin modified with natural plant oil and its preparation process, comprising the following steps:

[0071] S2.1. Weigh the following raw materials in parts by weight: 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;

[0072] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0073] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0074] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0075] 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 biodegradable bioresin modified with natural vegetable oil.

[0076] Wherein, the preparation process of modified corn oil is as follows:

[0077] S1.1. Weigh the following raw materials in parts by weight: 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;

[0078] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0079] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0080] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0081] Example 5: Sustainable biodegradable bioresin modified with natural vegetable oil and its preparation process, comprising the following steps:

[0082] S2.1. Weigh the following raw materials in parts by weight: 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;

[0083] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0084] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0085] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0086] 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 biodegradable bioresin modified with natural vegetable oil.

[0087] Wherein, the preparation process of modified corn oil is as follows:

[0088] S1.1. Weigh the following raw materials in parts by weight: 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;

[0089] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0090] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0091] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0092] Example 6: Sustainable biodegradable bioresin modified with natural vegetable oil and its preparation process, comprising the following steps:

[0093] S2.1. Weigh the following raw materials in parts by weight: 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;

[0094] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0095] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0096] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0097] 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 biodegradable bioresin modified with natural vegetable oil.

[0098] Wherein, the preparation process of modified corn oil is as follows:

[0099] S1.1. Weigh the following raw materials in parts by weight: 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;

[0100] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0101] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0102] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0103] Example 7: Sustainable biodegradable bioresin modified with natural plant oil and its preparation process, comprising the following steps:

[0104] S2.1. Weigh the following raw materials in parts by weight: 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;

[0105] S2.2. Add the modified corn oil to the reactor and stir at 150 rpm for 15 min. Then, 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.

[0106] 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 is completed, lower the temperature of the reactor to 60°C, add polyisocyanate, and stir at 300 rpm for 8 hours.

[0107] S2.4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 600 rpm, and stir for 60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 500 rpm for 30 minutes to obtain a mixture;

[0108] 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 biodegradable bioresin modified with natural vegetable oil.

[0109] Wherein, the preparation process of modified corn oil is as follows:

[0110] S1.1. Weigh the following raw materials in parts by weight: 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;

[0111] S1.2. Corn oil and N-butylpyridinium tetrafluoroborate were stirred at 150 rpm for 20 min at room temperature. Toluene was added, and the temperature was simultaneously increased to 120°C at a rate of 2°C / min. The mixture was stirred at 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 300 rpm for 30 min to remove the N-butylpyridinium tetrafluoroborate catalyst. The mixture was allowed to stand for 20 min, and filtered to obtain isomerized corn oil.

[0112] S1.3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at 150 rpm for 30 min at room temperature. Raise the temperature of the reaction system to 160°C at a rate of 3°C / min and stir at 500 rpm for 8 h to allow the isomerized corn oil and dimethyl fumarate to fully react.

[0113] 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 the process 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, a temperature of 60°C, and a time of 3 hours to remove moisture and low-boiling impurities to obtain modified corn oil.

[0114] Comparative Example 1

[0115] The method of Example 6 was adopted, but modified corn oil was not used. Instead, corn oil was directly used to prepare a sustainable biodegradable bioresin modified based on natural vegetable oil.

[0116] Comparative Example 2

[0117] The method of Example 6 was used to remove dimethyl fumarate during the preparation process of modified corn oil.

[0118] Comparative Example 3

[0119] The method of Example 6 was adopted, and grape seed oil was substituted for the modified corn oil.

[0120] The present invention prepares a sustainable biodegradable bioresin modified with natural vegetable oil by modifying corn oil. The performance index test items and test standards of the sustainable biodegradable bioresin modified with natural vegetable oil are as follows:

[0121] According to the national standard GB / T 1040.2, the specimen is clamped between the upper and lower clamps of the testing machine. An appropriate preload is applied to ensure that the specimen remains straight and does not deform. The testing machine stretches the specimen at a speed of 50mm / min to 500mm / min until the specimen breaks. The testing machine automatically records the force applied and the elongation of the specimen during the stretching process, plots the stress-strain curve, and calculates the tensile strength and elongation at break using formulas. A higher tensile strength indicates that the material has strong tensile resistance and can remain intact without breaking under large external forces. A higher elongation at break indicates that the material is not prone to sudden breakage when subjected to stress and can undergo large deformation before breaking.

[0122] According to the national standard GB / T 9341, the specimen is placed symmetrically on the support device of the testing machine. A bending load is applied at a rate of 2mm / min to 50mm / min through a loading head located in the middle of the specimen until the specimen breaks or reaches a predetermined maximum deflection. The testing machine automatically records the load and deflection changes during the loading process, plots the stress-strain curve, and calculates the bending strength using a formula. Bending strength is the ability of a material to resist damage under bending stress. A higher bending strength indicates that the material has strong bending resistance and is less likely to yield or break.

[0123] The above standards were used to test the sustainable biodegradable bioresins modified with natural plant oils prepared in Examples 1-7 and Comparative Examples 1-3. The obtained data are shown in Table 1:

[0124] Table 1 Performance data of bioresins of Examples 1-7 and Comparative Examples 1-3

[0125]

[0126] 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 bio-resin gradually increase. However, 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 bio-resin gradually decrease. Therefore, it can be seen that as the mass ratio of N-butylpyridinium tetrafluoroborate increases, the tensile strength, elongation at break, and flexural strength of the bio-resin are improved, but excessive increase may reduce the tensile strength, elongation at break, and flexural strength of the bio-resin.

[0127] 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 the bioresin. N-butylpyridinium tetrafluoroborate may, to a certain extent, induce the corn oil molecular chains to arrange more regularly during the reaction. When the mass ratio increases, the induction effect becomes 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, flexural strength and elongation at break; appropriately increasing the mass ratio of N-butylpyridinium tetrafluoroborate helps to improve the solubility between corn oil and other additives, making the entire system more uniform and stable. Good solubility can reduce phase separation, avoid weak areas, and enable the material to transfer stress more evenly when subjected to force, thereby improving mechanical properties such as tensile strength, flexural strength and elongation at break.

[0128] Furthermore, by comparing Examples 1-3, it can be seen that when the other components remain unchanged, only when the proportion of modified corn oil gradually increases, the tensile strength, elongation at break, and flexural strength of the bioresin gradually increase. It can be seen that the molecular chains of modified corn oil generally have a certain flexibility. When its proportion increases, the flexibility of the overall molecular chain of the bioresin is enhanced. When subjected to external force, the molecular chains can more easily orient and slip, thereby improving the elongation at break; at the same time, the flexibility of the molecular chain also helps to absorb and disperse impact energy, making the material less likely to break when bent, thereby improving the flexural strength; as the proportion of modified corn oil increases, it can be inserted between the molecular chains of the bioresin, reducing the interaction force between the molecular chains, and making the molecular chains move more freely, 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 bioresin can better adapt to deformation when bent, thereby improving the flexural strength; in addition, the modified corn oil has better compatibility and interfacial bonding with other components in the bioresin, and can form more physical or chemical bonding points between these components, which can effectively transfer stress to the entire material system, thereby improving the tensile strength, elongation at break, and flexural strength of the material.

[0129] Comparing Example 6 with Comparative Example 1, it can be seen that when corn oil is directly used to prepare the sustainable biodegradable bioresin modified based on natural vegetable oil without using modified corn oil, the tensile strength, elongation at break and flexural strength of the bioresin are significantly reduced.

[0130] Taking Example 6 as the optimal example and combining it with Comparative Example 2, it can be seen that when dimethyl fumarate is removed in the preparation process of modified corn oil, the tensile strength, elongation at break and flexural strength of the bio-resin are significantly reduced;

[0131] 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 improve the cross-linking density, thereby enhancing the hardness and wear resistance of the resin; however, after removing the dimethyl fumarate, the number of cross-linking points is greatly reduced, and the cross-linking density is reduced, resulting in a significant decrease in the tensile strength, flexural strength and elongation at break of the bio-resin; this is because the imperfection of the cross-linking network makes relative slip between the molecular chains more likely to occur. When subjected to tensile force, the molecular chains cannot work together well to resist the external force, 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 the dimethyl fumarate, the rigidity of the molecular chain is relatively increased, making it difficult for the material to deform when subjected to external force, and the ability to resist stretching and bending is reduced, resulting in a significant decrease in tensile strength, elongation at break and flexural strength.

[0132] 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;

[0133] The unsaturated fatty acids in grape seed oil are mainly linoleic acid and oleic acid. These fatty acids contain multiple double bonds with different positional 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 interaction 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 the bio-resin.

[0134] 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 to the above embodiments. The above embodiments and descriptions are merely preferred examples of the present invention and are not intended to limit the present invention. Various changes and improvements may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and improvements fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. Sustainable biodegradable bioresin modified from natural plant 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; Modified corn oil is prepared by a double bond isomerization reaction of corn oil with N-butylpyridinium tetrafluoroborate and then adding dimethyl fumarate; The preparation process of the modified corn oil is as follows: S1.

1. Weigh the following raw materials in parts by weight: 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. Stir corn oil and N-butylpyridinium tetrafluoroborate at room temperature at 100-150 rpm for 10-20 minutes, add toluene, and slowly raise the temperature to 80-120°C. Stir and react at 300-600 rpm for 2-6 hours. After the reaction, cool the reaction system to room temperature, add activated alumina, and stir at 200-300 rpm for 15-30 minutes to remove the N-butylpyridinium tetrafluoroborate catalyst. Let stand for 10-20 minutes, and filter to obtain isomerized corn oil. S1.

3. Add isomerized corn oil to a reaction vessel, add dimethyl fumarate, hydroquinone, and benzoyl peroxide, and stir at room temperature at 100-150 rpm for 15-30 minutes. Raise the temperature of the reaction system to 120-160°C at a rate of 2-3°C / minute and stir at 300-600 rpm for 3-8 hours to allow the isomerized corn oil and dimethyl fumarate to fully react. 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 moisture and low-boiling point impurities to obtain modified corn oil.

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

3. The sustainable biodegradable bioresin modified based on natural plant oil according to claim 1, characterized in that: In the above-mentioned S1.2, the particle size of the activated alumina is 1-3 mm.

4. The sustainable biodegradable bioresin modified based on natural plant oil according to claim 1, 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 minutes; after stirring is completed, let the separatory funnel stand to separate the aqueous phase, and repeat 3-5 times.

5. The sustainable biodegradable bioresin modified based on natural plant oil according to claim 1, 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.

6. A process for preparing a sustainably degradable bio-resin modified with natural vegetable oil, for preparing the sustainably degradable bio-resin modified with natural vegetable oil as claimed in any one of claims 1 to 5, characterized in that: The preparation process of the sustainable degradable bioresin modified with natural vegetable oil is as follows: S2.

1. Weigh the following raw materials in parts by weight: 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 to the reactor and stir at 100-150 rpm for 10-15 minutes; slowly add triethyl citrate dropwise and continue stirring at 100-150 rpm for 15-30 minutes to evenly disperse the triethyl citrate 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 300-600 rpm, and continue stirring for 2-6 hours to allow the modified corn oil to fully polymerize. After the polymerization reaction is completed, lower the temperature of the reactor to 60-80°C, add the crosslinking agent, and stir at 200-300 rpm for 3-8 hours. S2.

4. After the cross-linking reaction is completed, add the regenerated cellulose fibers to the reactor, increase the stirring speed to 400-800 rpm, and stir for 30-60 minutes to uniformly disperse the regenerated cellulose fibers; then add 2-hydroxy-4-n-octyloxybenzophenone and triphenyl phosphite, and continue stirring at 400-800 rpm for 15-30 minutes 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 biodegradable bioresin modified with natural plant oil.

7. The process for preparing a sustainable biodegradable bioresin modified with natural vegetable oil according to claim 6, 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.

8. The process for preparing a sustainable biodegradable bioresin modified with natural vegetable oil according to claim 6, characterized in that: In the above-mentioned S2.3, the cross-linking agent is polyisocyanate or hexamethylene diisocyanate.

9. The process for preparing a sustainable biodegradable bioresin modified with natural vegetable oil according to claim 6, 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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