1. The preparation method of the photocuring material is characterized by comprising the following steps: (1) adding vegetable oil and maleic anhydride into a reactor, wherein the molar ratio of the vegetable oil to the maleic anhydride is 1 (0.5-5), uniformly stirring, heating to 100-220 ℃, and reacting for 1-5 hours to obtain maleated vegetable oil; (2) performing alkali washing and acid washing on the obtained maleic anhydride vegetable oil to obtain a vegetable oil-based polycarboxylic acid compound; (3) adding glycidyl methacrylate, a catalyst and a polymerization inhibitor into the plant oil-based polycarboxylic acid compound, wherein the molar ratio of the glycidyl methacrylate to carboxyl in the plant oil-based polycarboxylic acid compound is (1-1.5): 1, the dosage of the catalyst is 0.5-3% of the total weight of the raw materials, and the dosage of the polymerization inhibitor is 0.5-2% of the total weight of the raw materials, heating to 50-130 ℃, and reacting for 1-5 hours to obtain a plant oil-based polyallylene ester prepolymer; (4) adding malic acid, a vinyl monomer and a catalyst into another reactor, wherein the molar ratio of the vinyl monomer to the malic acid is (2-3) to 1; the dosage of the catalyst is 0.5-3% of the total weight of the raw materials, the mixture is uniformly stirred and then heated to 30-100 ℃ for reaction for 5-30 h, and a malic acid base diluted monomer is obtained; (5) and (3) adding the synthesized malic acid base diluent monomer and photoinitiator into the plant oil-based poly (allyl ester) prepolymer synthesized in the step (3), wherein the using amount of the malic acid base diluent monomer is 0-30% of the mass of the prepolymer, the using amount of the photoinitiator is 0.5-1% of the total weight of the bio-based UV photosensitive resin, uniformly stirring, and removing bubbles to obtain the bio-based UV photosensitive resin.

2. The method for producing a photocurable material according to claim 1, wherein the vegetable oil in step (1) is at least one of tung oil, linseed oil, rubber seed oil, dehydrated castor oil, rapeseed oil, cornus wilsoniana seed oil, sunflower seed oil, cotton seed oil, soybean oil, and corn oil, and the molar ratio of the vegetable oil to the maleic anhydride is 1: 2.

3. The method for preparing a photocurable material according to claim 1, wherein the base in step (2) is at least one of sodium hydroxide, potassium hydroxide, and calcium hydroxide; the acid is at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.

4. The method for producing a photocurable material according to claim 1, wherein the molar ratio of the glycidyl methacrylate to the carboxyl group in the vegetable oil-based polycarboxylic acid compound in the step (3) is 1.5: 1; the catalyst is at least one of p-toluenesulfonic acid, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate and 4-dimethylaminopyridine, and the amount of the catalyst is 1% of the total weight of the raw materials; the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-methylphenol, and the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials.

5. The method for preparing a photocurable material according to claim 1, wherein the vinyl monomer in step (4) is at least one of allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate and glycidyl methacrylate, and the molar ratio of the vinyl monomer to malic acid is 2: 1.

6. The method for preparing a photocurable material according to claim 1, wherein the catalyst in step (4) is at least one of p-toluenesulfonic acid, DCC/DMAP, EDCI/DMAP, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate, and 4-dimethylaminopyridine, and the amount of the catalyst is 0.5% by weight based on the total weight of the raw materials.

7. The method for preparing a photocurable material according to claim 1, wherein the amount of the malic acid based diluent monomer used in step (5) is 30% by weight of the vegetable oil based poly (propenyl) ester prepolymer, the photoinitiator is at least one of Darocur 1173, Irgacure 184, Irgacure 651 and Irgacure 369, and the amount of the photoinitiator is 1% by weight of the total weight of the obtained bio-based UV photosensitive resin.

8. A photocurable material prepared by the process of any one of claims 1 to 7.

9. Use of the photocurable material of claim 8 in the preparation of wood ware and metal surface coating products.

Background

In modern society, organic coatings are widely used for decoration, protection and certain specific applications, such as antibiosis, antifouling, flame retardation and the like. Volatile Organic Chemicals (VOCs) are often included in conventional organic coatings to reduce the viscosity of the coatings, but this does not meet the increasing environmental demands. In the past decades, Ultraviolet (UV) curing technology has attracted attention because of its 5E characteristics of high efficiency, energy saving, wide adaptability, economy, environmental protection, etc. However, most of the UV curable resins reported so far are derived from non-renewable, environmentally polluting fossil energy sources. In addition, UV cured materials typically have a stable crosslinked network and cannot be reprocessed or recycled by melting as thermoplastic polymers do, thus resulting in waste of materials and environmental pollution.

A very effective strategy to achieve both recycling and rework is to introduce dynamic bonds in the UV cured material. Dynamic covalent polymers have a long history, and it has been found as early as 1946 that disulfide bonds in vulcanized rubber are always in a dynamic balance of broken bonds and formed bonds; the siloxane balance was found to be present in silicone rubber in 1954. But this has not received much attention. In recent years, with the introduction of various concepts such as "dynamers", "equivalent adaptive network (CAN)" and "visimers", dynamic compounds have been rapidly developed. Dynamic compounds have unique advantages over traditional thermosets, such as repairability and reworkability. Heretofore, numerous covalent bonds including Transesterification (TERs), carbamylation, disulfide bond formation, imidization, borate linkages, olefin metathesis, and the like have been employed in the design and assembly of dynamic covalent compounds. Of these, TERs are of great interest, primarily because of the large number of ester linkages present in the commercial thermosetting polymers commonly found today, such as epoxy resins, unsaturated polyester resins, acrylate resins, and the like. In recent years, TERs have been used to make recyclable UV curable materials (Nature communications,2018,9, 1831; ChemSumschem, 2019,12, 893-. However, the currently reported TERs-based UV-curable materials all require heat treatment at high temperature (>150 ℃) for a period of time, which limits their practical application in the UV coating industry; in addition, the bio-based content of the UV curable materials prepared is not generally high, which means that they still rely too much on fossil energy.

Disclosure of Invention

The technical problem to be solved is as follows: the invention provides a photocuring material and a preparation method and application thereof, aiming at overcoming the defects that the existing biobased photocuring material cannot be recycled and reprocessed, and the content of biobased materials is low.

The technical scheme is as follows: a preparation method of a light-cured material comprises the following preparation steps: (1) adding vegetable oil and maleic anhydride into a reactor, wherein the molar ratio of the vegetable oil to the maleic anhydride is 1 (0.5-5), uniformly stirring, heating to 100-220 ℃, and reacting for 1-5 hours to obtain maleated vegetable oil; (2) performing alkali washing and acid washing on the obtained maleic anhydride vegetable oil to obtain a vegetable oil-based polycarboxylic acid compound; (3) adding glycidyl methacrylate, a catalyst and a polymerization inhibitor into the plant oil-based polycarboxylic acid compound, wherein the molar ratio of the glycidyl methacrylate to carboxyl in the plant oil-based polycarboxylic acid compound is (1-1.5): 1, the dosage of the catalyst is 0.5-3% of the total weight of the raw materials, and the dosage of the polymerization inhibitor is 0.5-2% of the total weight of the raw materials, heating to 50-130 ℃, and reacting for 1-5 h to obtain a plant oil-based polyallyl ester prepolymer; (4) adding malic acid, a vinyl monomer and a catalyst into another reactor, wherein the molar ratio of the vinyl monomer to the malic acid is (2-3) to 1; the dosage of the catalyst is 0.5-3% of the total weight of the raw materials, the mixture is uniformly stirred and then heated to 30-100 ℃ for reaction for 5-30 h, and a malic acid base diluted monomer is obtained; (5) and (3) adding the synthesized malic acid base diluent monomer and photoinitiator into the plant oil-based poly (allyl ester) prepolymer synthesized in the step (3), wherein the using amount of the malic acid base diluent monomer is 0-30% of the mass of the prepolymer, the using amount of the photoinitiator is 0.5-1% of the total weight of the bio-based UV photosensitive resin, uniformly stirring, and removing bubbles to obtain the bio-based UV photosensitive resin.

The vegetable oil in the step (1) is at least one of tung oil, linseed oil, rubber seed oil, dehydrated castor oil, rapeseed oil, cornus wilsoniana seed oil, sunflower seed oil, cottonseed oil, soybean oil and corn oil, and the molar ratio of the vegetable oil to the maleic anhydride is 1: 2.

The alkali in the step (2) is at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide; the acid is at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.

The molar ratio of the glycidyl methacrylate to the carboxyl groups in the vegetable oil-based polycarboxylic acid compound in the step (3) is 1.5: 1; the catalyst is at least one of p-toluenesulfonic acid, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate and 4-dimethylaminopyridine, and the amount of the catalyst is 1% of the total weight of the raw materials; the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-methylphenol, and the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials.

The vinyl monomer in the step (4) is at least one of allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, hydroxyethyl methacrylate and glycidyl methacrylate, and the molar ratio of the vinyl monomer to the malic acid is 2: 1.

The catalyst in the step (4) is at least one of p-toluenesulfonic acid, DCC/DMAP, EDCI/DMAP, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate and 4-dimethylaminopyridine, and the dosage of the catalyst is 0.5% of the total weight of the raw materials.

The using amount of the malic acid base diluent monomer in the step (5) is 30% of the mass of the plant oil-based poly-propenyl ester prepolymer, the photoinitiator is at least one of Darocur 1173, Irgacure 184, Irgacure 651 and Irgacure 369, and the using amount of the photoinitiator is 1% of the total weight of the obtained bio-based UV photosensitive resin.

The light-cured material prepared by the method.

The light-cured material is applied to the preparation of woodware and metal surface coating products.

Has the advantages that: (1) the UV curing material synthesized by the invention has high biobased content and excellent mechanical, thermal, coating film performance, self-repairing and reprocessing performances. (2) The synthesis method comprises the steps of modifying the vegetable oil by maleic anhydride, then opening the ring of the synthesized maleic anhydride vegetable oil by alkaline washing and acid washing, and then performing epoxy ring opening by glycidyl methacrylate to obtain a photocuring prepolymer; finally, malic acid and vinyl monomer are esterified to obtain malic acid base diluent monomer and photoinitiator are evenly dispersed into the synthesized photocuring prepolymer, and the UV curing material can be obtained through photocuring. The method is easy to operate and simple in process.

Drawings

FIG. 1 is FT-IR spectrogram of tung oil-based acrylate prepolymer;

FIG. 2 is a FT-IR spectrum of malic acid based diluent monomer.

Detailed Description

The following examples are provided as further illustration of the invention and are not to be construed as limitations or limitations of the invention. The present invention will be described in more detail with reference to examples.

Example 1

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding a photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1 percent of the total weight of the photosensitive resin) into the generated plant oil-based propenyl ester prepolymer, and uniformly stirring to obtain the photosensitive resin.

Example 2

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 3

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 20% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 4

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 30% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 5

(1) Adding linseed oil and maleic anhydride (the molar ratio of the maleic anhydride to the linseed oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 6

(1) Adding rubber seed oil and maleic anhydride (the molar ratio of the maleic anhydride to the rubber seed oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 7

(1) Adding corn oil and maleic anhydride (the molar ratio of the maleic anhydride to the corn oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 8

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), p-toluenesulfonic acid serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, and heating to 100 ℃ for reaction for 3 hours to obtain a vegetable oil-based polypropylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 9

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the plant oil-based polycarboxylic acid is 1:1), N-dimethylbenzylamine (the amount of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol (the amount of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified plant oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a plant oil-based polypropylenyl ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 10

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, hydroxyethyl acrylate (the molar ratio of the hydroxyethyl acrylate to the malic acid is 2:1) and a catalyst p-toluenesulfonic acid (the amount of the catalyst is 0.5% of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20h to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 11

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, hydroxyethyl methacrylate (the molar ratio of hydroxyethyl methacrylate to malic acid is 2:1) and p-toluenesulfonic acid as a catalyst (the amount of the catalyst is 0.5% of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃, and reacting for 20h to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl) ester prepolymer) and the photoinitiator Darocur 1173 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl) ester prepolymer to obtain the photosensitive resin.

Example 12

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl ester) prepolymer) and the photoinitiator Irgacure 184 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl ester) prepolymer to obtain the photosensitive resin.

Example 13

(1) Adding tung oil and maleic anhydride (the molar ratio of the maleic anhydride to the tung oil is 2:1) into a reactor, uniformly stirring, heating to 160 ℃, and reacting for 2 hours to obtain maleated vegetable oil;

(2) performing alkali washing (1mol/L NaOH) and acid washing (1mol/L HCl) on the obtained maleic anhydride vegetable oil, and finally washing the obtained maleic anhydride vegetable oil to be neutral by using a saturated sodium chloride aqueous solution to obtain a vegetable oil-based polycarboxylic acid compound;

(3) adding glycidyl methacrylate (the molar ratio of the glycidyl methacrylate to carboxyl in the vegetable oil-based polycarboxylic acid is 1:1), triphenylphosphine serving as a catalyst (the dosage of the catalyst is 1 percent of the total weight of the raw materials) and p-methoxyphenol serving as a polymerization inhibitor (the dosage of the polymerization inhibitor is 0.5 percent of the total weight of the raw materials) into the purified vegetable oil-based polycarboxylic acid compound, heating to 100 ℃, and reacting for 3 hours to obtain a vegetable oil-based polyallylene ester prepolymer;

(4) adding malic acid, methallyl alcohol (the molar ratio of the methallyl alcohol to the malic acid is 2:1) and a catalyst of p-toluenesulfonic acid (the amount of the catalyst is 0.5 percent of the total weight of the raw materials) into another reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a malic acid base diluted monomer;

(5) uniformly dispersing the synthesized malic acid base diluent monomer (the dosage is 10% of the weight of the plant oil-based poly (propenyl ester) prepolymer) and the photoinitiator Irgacure 651 (the dosage of the photoinitiator is 1% of the total weight of the photosensitive resin) into the synthesized plant oil-based poly (propenyl ester) prepolymer to obtain the photosensitive resin.

Example 14

Respectively weighing 20g of the resin of the embodiment 1-13, stirring for 20min, degassing, pouring into a self-made polytetrafluoroethylene mold or coating on a tinplate, and forming a film through UV curing. Tensile property: the mechanical properties of the photocurable film were measured according to ASTM D638-2008 using a model SANS7 CMT-4304 universal tester (Shenzhen New Sansi instruments, Inc.), with a gauge length of 50mm and a tensile rate of 5.0 mm/min. The sample size was 80X 10X 1mm³. Glass transition temperature: the dynamic thermomechanical properties were determined using a Q800 solid analyser (TA, USA). Thermogravimetric analysis: the thermo-mechanical stability of the photo-cured film was measured using a STA 409PC thermogravimetric analyzer (Netzsch, Germany). The heating interval is 40-600 ℃, and the heating rate is 15 ℃/min. The performance of the coating film is as follows: the adhesion of the coating film is tested according to the method of GB/T9286-1998, the best grade 1 and the worst grade 7; testing the flexibility of the coating film according to the method of GB/T1731-93, wherein the minimum diameter of the shaft rod is 2mm, and the smaller the diameter of the shaft rod is, the better the flexibility is; the hardness of the paint film was determined according to GB/T6739-2006, 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B, 6B, with 6H being the hardest and 6B being the softest. Content of bio-based: according to the definition of the U.S. department of agriculture: "biobased content of a material means the biobased carbon content of the material or product as a percentage of the total organic carbon weight (mass) of the product". Self-repairing efficiency: and the scratch repair efficiency is calculated by observing the reduction ratio of the scratch width before and after repair by using an ICC50W Leica optical microscope. The test results of each example are shown in Table 1.

TABLE 1 Primary coating Performance indicators for resin samples of examples 1-13

As can be seen from the data in the table, the bio-based UV curing material prepared by the invention has high bio-based content, excellent mechanical, thermal, coating film performance, self-repairing and reprocessing performances, and can be used as a woodware and metal surface coating.

The above examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.