阅读说明：本技术 一种可自修复的含呋喃基团的生物基不饱和聚酯树脂及其制备方法和应用 (Self-repairable furan group-containing bio-based unsaturated polyester resin and preparation method and application thereof ) 是由 林绍建 兰建武 尚娇娇 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种可自修复的含呋喃基团的生物基不饱和聚酯树脂及其制备方法和应用,本发明首先通过于特定溶剂、催化剂种类、催化剂用量、反应物投料比、酸的种类及溶度等反应条件下,以高收率(收率可达95％)制备得到蒽基二元醇类化合物,然后以蒽基二元醇类化合物、2,5-呋喃二甲酸、碳碳双键二元羧酸类化合物和脂肪二元醇类化合物作为反应单体原料,采用熔融聚合的方法获得具有自修复功能的生物基不饱和聚酯,最后以生物基不饱和聚酯为主体,以苯乙烯、衣康酸等为稀释剂,加入光引发剂得到UV可固化的自修复生物基不饱和聚酯树脂涂料,有效解决了现有生物基不饱和聚酯树脂涂料中存在的膜修补性能差、耐用性能差和使用寿命短的问题。(The invention discloses a self-repairing bio-based unsaturated polyester resin containing furan groups and a preparation method and application thereof, firstly, an anthracene-based diol compound is prepared with high yield (the yield can reach 95%) under the reaction conditions of specific solvent, catalyst type, catalyst dosage, reactant charge ratio, acid type, solubility and the like, then the anthracene-based diol compound, 2, 5-furandicarboxylic acid, carbon-carbon double bond dicarboxylic acid compound and fatty diol compound are used as reaction monomer raw materials to obtain the bio-based unsaturated polyester with the self-repairing function by adopting a melt polymerization method, and finally the bio-based unsaturated polyester is used as a main body, styrene, itaconic acid and the like are used as diluents, and a photoinitiator is added to obtain the UV curable bio-based unsaturated polyester resin coating, so that the problems of poor film repairing performance, and poor film repairing performance existing in the existing bio-based unsaturated polyester resin coating are effectively solved, Poor durability and short service life.)

1. The self-repairable furan group-containing bio-based unsaturated polyester resin is characterized by having the following structural formula:

wherein a is a natural number in 2-6; b is 0,1 or 2.

2. The preparation method of the self-repairable furan group-containing bio-based unsaturated polyester resin of claim 1, characterized by comprising the following steps:

step (1): adding 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid, 9-anthryl methanol, a catalyst and a solvent into a reaction container, reacting for 15-30 hours at room temperature, and separating and purifying a reaction system after the reaction is finished to obtain an intermediate product; wherein the molar ratio of the 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid to the 9-anthryl methanol is 1-3: 1-3; the molar use ratio of the 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid to the catalyst is 1: 1-2;

step (2): adding the intermediate product obtained in the step (1) and acid into a reaction container for hydrolysis reaction to obtain an anthracene-based diol compound;

and (3): adding the anthracene-based diol compound obtained in the step (2), 2, 5-furandicarboxylic acid, carbon-carbon double bond dicarboxylic acid compound, fatty diol compound, catalyst, antioxidant and polymerization inhibitor into a reaction device, and performing esterification and polycondensation to obtain unsaturated polyester resin; wherein, the reaction conditions in the esterification stage are as follows: reacting in an inert gas protective atmosphere at the temperature of 140-230 ℃ for 1-3 hours; the reaction conditions in the polycondensation stage are: carrying out reaction under the vacuum of 10-500 Pa, wherein the reaction temperature is 180-290 ℃, and the reaction time is 2-5 hours;

the intermediate product has the following structural formula:

the structural formula of the anthracene-based diol compound is shown as follows:

3. the method for preparing the self-repairable furan group-containing bio-based unsaturated polyester resin of claim 2, wherein the catalyst in the step (1) is at least one of dicyclohexylcarbodiimide, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 4-dimethylaminopyridine.

4. The preparation method of the self-repairable furan group-containing bio-based unsaturated polyester resin as claimed in claim 2 or 3, wherein the catalyst is a mixed catalyst composed of DCC and DMAP or a mixed catalyst composed of DBU and DMAP; wherein the molar weight of DCC or DBU is equal to that of 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid, and the molar weight of DMAP is 0.1-0.8 times that of DCC or DBU.

5. The method for preparing self-repairable furan-group-containing bio-based unsaturated polyester resin according to claim 2, wherein in the step (3), the molar amount of 2, 5-furandicarboxylic acid is 30 to 70 percent of the total molar amount of 2, 5-furandicarboxylic acid and carbon-carbon double bond dicarboxylic acid compounds, the molar amount of carbon-carbon double bond dicarboxylic acid compounds is 30 to 70 percent of the total molar amount of 2, 5-furandicarboxylic acid and carbon-carbon double bond dicarboxylic acid compounds, the molar amount of fatty diol compounds is 200 to 400 percent of the total molar amount of 2, 5-furandicarboxylic acid and carbon-carbon double bond dicarboxylic acid compounds, the molar amount of anthracenediol compounds is 5 to 55 percent of the total molar amount of 2, 5-furandicarboxylic acid and carbon-carbon double bond dicarboxylic acid compounds, and the molar amount of catalyst is 5 to 55 percent of anthracenediol compounds, Five to two thousandths of the total molar amount of the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, the molar amount of the antioxidant accounts for two to five thousandths of the total molar amount of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, and the molar amount of the polymerization inhibitor accounts for two to one thousandth of the total molar amount of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound.

6. The preparation method of the self-repairable furan group-containing bio-based unsaturated polyester resin of claim 2 or 5, wherein in the step (3), the carbon-carbon double bond dicarboxylic acid compound is citraconic acid, fumaric acid or itaconic acid; the aliphatic diol compound in the step (3) is ethylene glycol, propylene glycol, butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol or 1, 8-octanediol; the catalyst in the step (3) is tetrabutyl titanate, zinc acetate, manganese acetate, germanium dioxide, antimony trioxide or antimony acetate; the antioxidant in the step (3) is an antioxidant 1010, an antioxidant 1076, an antioxidant CA or an antioxidant 164; and (3) the polymerization inhibitor is hydroquinone.

7. The self-repairable furan group-containing bio-based unsaturated polyester resin of claim 1, applied in a coating.

8. The UV-cured and self-repairable bio-based unsaturated polyester resin coating is characterized in that the self-repairable furan group-containing bio-based unsaturated polyester resin of claim 1 is used as a characteristic structural component.

9. The preparation method of the UV-cured and self-repairable bio-based unsaturated polyester resin coating of claim 8, which comprises the following steps:

stirring and mixing the self-repairable furan group-containing bio-based unsaturated polyester resin, the diluent and the photoinitiator uniformly, and irradiating the mixture for 20 to 180 minutes under ultraviolet light to finish curing to obtain a UV-cured and self-repairable bio-based unsaturated polyester resin coating; wherein, the molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin accounts for 30-70% of the molar total amount of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, the molar weight of the diluent accounts for 30-70% of the molar total amount of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, and the molar weight of the photoinitiator accounts for 0.2-1.5% of the molar weight of the diluent.

10. The method of claim 9, wherein the diluent is at least one of styrene, dimethyl itaconate and divinylbenzene, and the photoinitiator is ethyl 4-dimethylaminobenzoate, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

Technical Field

The invention relates to the technical field of unsaturated polyester resin coatings, in particular to self-repairable furan group-containing bio-based unsaturated polyester resin and a preparation method and application thereof.

Background

Coating technology based on functional coatings is considered one of the simplest and most efficient means of modifying and protecting substrate materials today. Unsaturated Polyester Resin (UPRs) coatings were one of the earliest coating varieties and have been widely used in the coating industry due to their high hardness, high gloss, good fullness, low cost, and ease of processing. However, with the continuous depletion of global petroleum resources and the increasing awareness of environmental protection, the traditional petroleum-based UPRs coating cannot meet the demand of social development. Therefore, the development of environment-friendly UPRs coating has great practical significance and social value to the whole coating industry.

In recent years, researchers and enterprises have favored the construction of environmentally friendly UPRs coatings using bio-based diols and diacids. For example, unsaturated polyesters are prepared based on bio-based raw materials succinic acid, 1, 4-butanediol and cis-hexadiene diacid, and UPRs coatings based on the unsaturated polyesters exhibit good adhesion and coating effects. Notably, UPRs coatings are currently prepared primarily using bio-based aliphatic dibasic acids instead of petroleum-based phthalic acids. However, the lack of a rigid structure in the coating causes a decrease in the thermal and mechanical properties of the coating film. Also, similar to traditional petroleum-based UPRs coatings, the currently developed bio-based UPRs coatings face a common bottleneck problem: the film repair performance is poor, and the damaged film layer has marks after being repaired. In practical application, the coating material is acted by external force and external environment for a long time in the using process, and cracks are easy to appear on the surface of the coating material, so that the damage of the coating is accelerated, and the service life of the coating is obviously shortened.

Disclosure of Invention

Aiming at the defects, the invention aims to provide a self-repairable furan group-containing bio-based unsaturated polyester resin, a preparation method and application thereof, which can effectively solve the problems of poor film repairing performance, poor durability and short service life of the existing bio-based UPRs coating.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a self-repairable furan group-containing bio-based unsaturated polyester resin, which has the following structural formula:

wherein a is a natural number in 2-6; b is 0,1 or 2; in the structural formula, "/" represents random copolymerization.

The self-repairable furan group-containing bio-based unsaturated polyester resin is obtained by an uncontrollable polymerization method, and the repeating units are not calculated, i.e. the values of n, m, z and k in the structural formula are not determined.

The invention also provides a preparation method of the self-repairable furan group-containing bio-based unsaturated polyester resin, which specifically comprises the following steps:

step (1): adding 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid, 9-anthryl methanol, a catalyst and a solvent into a reaction container, reacting for 15-30 hours at room temperature, and separating and purifying a reaction system after the reaction is finished to obtain an intermediate product; wherein the molar ratio of the 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid to the 9-anthryl methanol is 1-3: 1-3; the molar use ratio of the 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid to the catalyst is 1: 1-2;

step (2): adding the intermediate product obtained in the step (1) and acid into a reaction container for hydrolysis reaction to obtain an anthracene-based diol compound;

and (3): adding the anthracene-based diol compound obtained in the step (2), 2, 5-furandicarboxylic acid, carbon-carbon double bond dicarboxylic acid compound, fatty diol compound, catalyst, antioxidant and polymerization inhibitor into a reaction device, and performing esterification and polycondensation to obtain unsaturated polyester resin; wherein, the reaction conditions in the esterification stage are as follows: reacting in an inert gas protective atmosphere at the temperature of 140-230 ℃ for 1-3 hours; the reaction conditions in the polycondensation stage are: carrying out reaction under the vacuum of 10-500 Pa, wherein the reaction temperature is 180-290 ℃, and the reaction time is 2-5 hours;

the intermediate product has the following structural formula:

the structural formula of the anthracene-based diol compound is shown as follows:

further, in the step (1), the molar ratio of the 2,2, 5-trimethyl-1, 3-dioxane-5-carboxylic acid to the 9-anthrylmethanol is 1.5-2.5: 1.

Further, in the step (1), the catalyst is at least one of Dicyclohexylcarbodiimide (DCC), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 4-Dimethylaminopyridine (DMAP).

Further, the catalyst in the step (1) is a mixed catalyst consisting of DCC and DMAP or a mixed catalyst consisting of DBU and DMAP; wherein the molar weight of DCC or DBU is equal to that of 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid, and the molar weight of DMAP is 0.1-0.8 times that of DCC or DBU.

Further, the catalyst in the step (1) is preferably a mixed catalyst composed of DCC and DMAP in a molar ratio of 2: 1.

Further, in the step (1), the solvent is dichloromethane, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide or ethanol; dichloromethane is preferred.

Further, the acid in the step (2) is hydrochloric acid with a solubility of 0.2-1M, sulfuric acid with a solubility of 0.2-1M or acetic acid with a solubility of 0.2-1M.

Further, in the step (3), the molar amount of the 2, 5-furandicarboxylic acid accounts for 30-70% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the carbon-carbon double bond dicarboxylic acid compound accounts for 30-70% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the fatty diol compound accounts for 200-400% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the anthracenediol compound accounts for 5-55% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, and the molar amount of the catalyst accounts for five to two thousandths of the total molar amount of the anthracenediol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, the molar weight of the antioxidant accounts for two to five ten thousandths of the total molar weight of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, and the molar weight of the polymerization inhibitor accounts for two to one thousandth of the total molar weight of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound.

Further, the dicarboxylic acid compound with carbon-carbon double bond in the step (3) is citraconic acid, fumaric acid or itaconic acid.

Further, in the step (3), the aliphatic diol compound is ethylene glycol, propylene glycol, butylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol or 1, 8-octanediol.

Further, in the step (3), the catalyst is tetrabutyl titanate, zinc acetate, manganese acetate, germanium dioxide, antimony trioxide or antimony acetate.

Further, the antioxidant in the step (3) is antioxidant 1010, antioxidant 1076, antioxidant CA or antioxidant 164.

Further, in the step (3), the polymerization inhibitor is preferably hydroquinone.

The invention also provides application of the self-repairable furan group-containing bio-based unsaturated polyester resin in a coating.

The invention also provides a UV-cured and self-repairable bio-based unsaturated polyester resin coating, which adopts the self-repairable bio-based unsaturated polyester resin containing furan groups as a characteristic structural component.

The invention also provides a preparation method of the UV-cured and self-repairable bio-based unsaturated polyester resin coating, which specifically comprises the following steps:

stirring and mixing the self-repairable furan group-containing bio-based unsaturated polyester resin, the diluent and the photoinitiator uniformly, and irradiating the mixture for 20 to 180 minutes under ultraviolet light to finish curing to obtain a UV-cured and self-repairable bio-based unsaturated polyester resin coating; wherein, the molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin accounts for 30-70% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, the molar weight of the diluent accounts for 30-70% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, and the molar weight of the photoinitiator accounts for 0.2-1.5% of the molar weight of the diluent.

Further, the diluent is at least one of styrene, dimethyl itaconate and divinylbenzene.

Further, the photoinitiator is ethyl 4-dimethylaminobenzoate, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-methanone or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

The invention has the following advantages:

1. the invention provides a self-repairable furan group-containing bio-based unsaturated polyester resin, which is characterized in that a bio-based dibasic acid-2, 5-furandicarboxylic acid is adopted to replace a traditional petroleum-based diphenyl acid monomer, and an anthracene-based dihydric alcohol compound with a self-repairing function is introduced, so that the furan group-based unsaturated bio-based polyester has a self-repairing performance, and when the furan group-based unsaturated polyester resin is applied to a coating, the problems of poor film repairing performance, poor durability and short service life in the existing bio-based unsaturated polyester coating can be effectively solved.

2. The invention provides a preparation method of the self-repairable furan group-containing bio-based unsaturated polyester resin, which comprises the steps of preparing an anthracene-based dihydric alcohol compound with high yield (the yield can reach 95%) under reaction conditions of specific solvents, catalyst types, catalyst dosage, reactant charge ratio, acid types, solubility and the like, and then taking the anthracene-based dihydric alcohol compound, 2, 5-furandicarboxylic acid, a carbon-carbon double bond dicarboxylic acid compound and a fatty dihydric alcohol compound as reaction monomer raw materials to obtain the bio-based unsaturated polyester resin with the self-repairing function by a melt polymerization method. The preparation method has the characteristics of simple operation, high product yield, environmental protection and the like through the selection of reaction parameters such as the catalyst, the reaction dosage ratio and the like, and has practical application value.

3. The molar ratio of the 2, 5-furandicarboxylic acid to the carbon-carbon double bond dicarboxylic acid compound can be adjusted in the preparation process of the self-repairable furan group-containing bio-based unsaturated polyester resin, materials with different mechanical properties and thermal properties can be adjusted, and the rigidity and the thermal stability of the 2, 5-furandicarboxylic acid are better than those of the carbon-carbon double bond dicarboxylic acid, so that the content of the 2, 5-furandicarboxylic acid is increased, the thermal properties and the mechanical properties of the product are also improved, but the content of the carbon-carbon double bond dicarboxylic acid compound is too low, so that unsaturated bonds in the obtained polymer are reduced, and the subsequent UV curing and self-repairable bio-based unsaturated polyester resin coating can not be prepared through UV curing.

4. The invention provides a UV-cured and self-repairable bio-based unsaturated polyester resin coating, which is prepared by taking self-made self-repairable bio-based unsaturated polyester as a main body, taking styrene, itaconic acid and the like as diluents and adding a certain proportion of photoinitiator; the UV-cured and self-repairable bio-based unsaturated polyester resin coating can perform self-repairing after being damaged by external force, and the self-repairing performance of the UV-cured and self-repairable bio-based unsaturated polyester resin coating is improved along with the increase of the content of the anthracene-based diol structure in the cured resin. The content of the anthracene-based diol structure in the bio-based unsaturated polyester resin coating prepared by the invention is 5-55%, and the self-repairing efficiency of the corresponding product is 10-85%.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The embodiment provides a preparation method of a self-repairable furan group-containing bio-based unsaturated polyester resin, which specifically comprises the following steps:

step (1): adding 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid (1mmol), 9-anthryl methanol, a catalyst and a solvent into a reaction vessel, reacting for 20 hours at room temperature, and separating and purifying a reaction system after the reaction is finished to obtain an intermediate product; wherein the molar ratio of 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid to 9-anthryl methanol is 2: 1; the molar use ratio of the 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid to the catalyst is 1: 1-2;

step (2): adding the intermediate product obtained in the step (1) and acid into a reaction container for hydrolysis reaction to obtain an anthracene-based diol compound;

and (3): adding the anthracene-based diol compound obtained in the step (2), 2, 5-furandicarboxylic acid, carbon-carbon double bond dicarboxylic acid compound, fatty diol compound, catalyst, antioxidant and polymerization inhibitor into a reaction device, and performing esterification and polycondensation to obtain unsaturated polyester resin; wherein, the reaction conditions in the esterification stage are as follows: reacting under the protection of inert gas at 200 ℃ for 2 hours; the reaction conditions in the polycondensation stage are: carrying out reaction under the vacuum of 100Pa, wherein the reaction temperature is 250 ℃, and the reaction time is 2 hours;

the intermediate product has the following structural formula:

the structural formula of the anthracene-based diol compound is shown as follows:

wherein, the catalyst in the step (1) is a mixed catalyst consisting of DCC and DMAP, the addition amount of DCC is equal to that of 2,2, 5-trimethyl-1, 3-dioxane-5-formic acid, and the molar weight of DMAP is 0.1-0.5 times that of DCC; the solvent in the step (1) is dichloromethane; the acid in the step (2) is hydrochloric acid with the solubility of 0.5M; in the step (3), the molar amount of the 2, 5-furandicarboxylic acid accounts for 70% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the carbon-carbon double bond dicarboxylic acid compound accounts for 30% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the fatty diol compound accounts for 400% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the anthracene-based diol compound accounts for 30% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the catalyst accounts for one thousandth of the total molar amount of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, and the molar amount of the antioxidant accounts for one thousandth of the anthracene-based diol compound, The molar amount of the polymerization inhibitor accounts for two thousandths of the total molar amount of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound; the dicarboxylic acid compound with carbon-carbon double bonds in the step (3) is fumaric acid; in the step (3), the aliphatic diol compound is butanediol; the catalyst in the step (3) is tetrabutyl titanate; the antioxidant in the step (3) is an antioxidant 164; in the step (3), the polymerization inhibitor is hydroquinone.

The synthetic route of the anthracenyl diol compound in the example is as follows:

the synthetic route for preparing the self-repairable furan group-containing bio-based unsaturated polyester resin by using the anthracene-based diol compound is as follows:

in this example, the final yield of the anthracene-based diol compound is 95%, and the final yield of the self-repairable furan group-containing bio-based unsaturated polyester resin is 89%.

Example 2

The present example provides a method for preparing a self-repairable furan group-containing bio-based unsaturated polyester resin, which is different from example 1 only in that: in the step (1), the solvent is tetrahydrofuran; the acid in the step (2) is acetic acid with the solubility of 1M; in the step (3), the molar amount of the 2, 5-furandicarboxylic acid accounts for 30% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the carbon-carbon double bond dicarboxylic acid compound accounts for 70% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the fatty diol compound accounts for 200% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the anthracene-based diol compound accounts for 10% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the catalyst accounts for five ten-thousandths of the total molar amount of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, and the molar amount of the antioxidant accounts for five ten-thousandths of the anthracene-based diol compound, Five ten-thousandths of the total molar amount of the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound, wherein the molar amount of the polymerization inhibitor accounts for one percent of the total molar amount of the anthracene-based diol compound, the 2, 5-furandicarboxylic acid, the carbon-carbon double bond dicarboxylic acid compound and the fatty diol compound; the dicarboxylic acid compound with carbon-carbon double bonds in the step (3) is citraconic acid; in the step (3), the aliphatic diol compound is 1, 7-heptanediol; the catalyst in the step (3) is manganese acetate; an antioxidant 1076 in the step (3); the rest steps and parameters are the same.

In this example, the final yield of the anthracene-based diol compound is 88%, and the final yield of the self-repairable furan group-containing bio-based unsaturated polyester resin is 82%.

Example 3

The present example provides a method for preparing a self-repairable furan group-containing bio-based unsaturated polyester resin, which is different from example 1 only in that: the solvent in the step (1) is N, N-dimethylformamide; the acid in step (2) is sulfuric acid with a solubility of 0.2M; in the step (3), the molar amount of the 2, 5-furandicarboxylic acid accounts for 60% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the carbon-carbon double bond dicarboxylic acid compound accounts for 40% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the aliphatic diol compound accounts for 350% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, the molar amount of the anthracenyl diol compound accounts for 55% of the total molar amount of the 2, 5-furandicarboxylic acid and the carbon-carbon double bond dicarboxylic acid compound, and the carbon-carbon double bond dicarboxylic acid compound in the step (3) is itaconic acid; in the step (3), the aliphatic diol compound is butanediol, and the rest steps and parameters are the same.

In this example, the final yield of the anthracene-based diol compound is 90%, and the final yield of the self-repairable furan group-containing bio-based unsaturated polyester resin is 81%.

Example 4

The embodiment provides a preparation method of a UV-cured and self-repairable bio-based unsaturated polyester resin coating, which specifically comprises the following steps:

uniformly stirring and mixing the self-repairable furan group-containing bio-based unsaturated polyester resin prepared in the embodiment 1, a diluent and a photoinitiator, and irradiating the mixture for 100min under ultraviolet light to finish curing to obtain a UV-cured and self-repairable bio-based unsaturated polyester resin coating; wherein the molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin accounts for 30% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, the molar weight of the diluent accounts for 70% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, and the molar weight of the photoinitiator accounts for 1% of the molar weight of the diluent; wherein the diluent is styrene, and the photoinitiator is ethyl 4-dimethylaminobenzoate.

The content of the anthracene-based diol structure in the UV-cured and self-repairable bio-based unsaturated polyester resin coating is 5%, and the self-repairing efficiency of the corresponding product is 10%.

Example 5

The embodiment provides a preparation method of a UV-cured and self-repairable bio-based unsaturated polyester resin coating, which specifically comprises the following steps:

uniformly stirring and mixing the self-repairable furan group-containing bio-based unsaturated polyester resin prepared in the embodiment 1, a diluent and a photoinitiator, and irradiating the mixture for 20min under ultraviolet light to finish curing to obtain a UV-cured and self-repairable bio-based unsaturated polyester resin coating; wherein the molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin accounts for 50% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, the molar weight of the diluent accounts for 50% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, and the molar weight of the photoinitiator accounts for 1.5% of the molar weight of the diluent; wherein, the diluent is itaconic acid dimethyl ester, and the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.

The content of the anthracene-based diol structure in the UV-cured and self-repairable bio-based unsaturated polyester resin coating prepared by the embodiment is 25%, and the self-repairing efficiency of the corresponding product is 65%.

Example 6

The embodiment provides a preparation method of a UV-cured and self-repairable bio-based unsaturated polyester resin coating, which specifically comprises the following steps:

uniformly stirring and mixing the self-repairable furan group-containing bio-based unsaturated polyester resin prepared in the embodiment 1, a diluent and a photoinitiator, and irradiating the mixture for 180min under ultraviolet light to finish curing to obtain a UV-cured and self-repairable bio-based unsaturated polyester resin coating; wherein the molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin accounts for 70% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, the molar weight of the diluent accounts for 30% of the total molar weight of the self-repairable furan group-containing bio-based unsaturated polyester resin and the diluent, and the molar weight of the photoinitiator accounts for 0.2% of the molar weight of the diluent; wherein the diluent is divinylbenzene, and the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.

The content of the anthracene-based diol structure in the UV-cured and self-repairable bio-based unsaturated polyester resin coating is 55%, and the self-repairing efficiency of the corresponding product is 85%.

In conclusion, the UV-cured and self-repairable bio-based unsaturated polyester resin coating provided by the invention has the advantages that the self-repairing performance of the coating is endowed by introducing the anthracene-based diol of the self-repairing group into the main chain of the polymer, and the coating has better durability and service life. Meanwhile, the self-repairing performance of the resin is improved along with the increase of the structure content of the anthracene-based diol in the cured resin.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to supplement or replace the specific embodiments described by those skilled in the art without inventive faculty.