CN114085353B - Photo-thermal dual-curing resin and preparation method thereof - Google Patents
Photo-thermal dual-curing resin and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer synthesis, and particularly relates to photo-thermal dual-curing resin and a preparation method thereof. The invention adopts a synthesis mode of 'first nucleus and then arm', diisocyanate and micromolecular polyol react to form a nucleus firstly, and dihydric alcohol directly connects the nuclei in an arm mode, so that the synthesis mode is easier to obtain a hyperbranched structure, the nucleus is equivalent to a hard segment, and the arm is equivalent to a soft segment, and can form a structure similar to a thermoplastic elastomer, thereby having high elasticity and high strength and being capable of resisting impact and abrasion of external force.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to photo-thermal dual-curing resin and a preparation method thereof.
Background
The super-hydrophilic surface has strong interaction force with water, and the water drop can be completely spread on the super-hydrophilic surface in a short time, so that the contact angle is equal to or close to 0 degrees, and the super-hydrophilic surface has very wide application prospect in the fields of self-cleaning, diversion, pollution prevention, biological consumables and the like, and is one of hot spots of current research. The method for realizing super-hydrophilicity is a chemical modification method (such as plasma treatment) or a surface coating method, but both the preparation methods have some problems, the chemical modification method needs expensive instruments and equipment or complex process flows, is easily influenced by external conditions (light, heat, oxygen and the like), and the application field is still to be developed. Surface coating processes have at the earliest relied on hydrophilic surfactants to provide hydrophilic properties, have poor durability, are susceptible to failure when exposed to water, and are increasingly replaced by hydrophilic resins. There are thermosetting hydrophilic resins and UV (ultraviolet) light-curable hydrophilic resins depending on the curing mode. Although thermosetting hydrophilic resins can provide good abrasion resistance, they require long curing time and high energy consumption for solvent evaporation, and are low in production efficiency. Whereas UV (ultraviolet) light-curable hydrophilic resins generally have a higher light transmittance than the thermal curing type, can be cured instantaneously under ultraviolet light, and are very suitable for continuous industrial production, but their abrasion resistance is generally lower than that of heat-curable coatings.
In order to overcome the above problems, several researchers have proposed a photo-thermal dual curing method, which combines the convenience of photo-curing with good wear resistance of thermal curing, and gives play to the respective advantages. CN104087137, which is a mixture of UV resin and inorganic siloxane, respectively implements photo-curing and thermal curing functions, which are implemented by single curing resin, respectively, and the photo-curing resin and the thermal curing resin are only physically connected, and no chemical bond is formed, so that the performance superposition effect is not obvious. CN107400407 adopts a synthesis mode of "arm first and core second", diisocyanate reacts with dihydric alcohol first to form arms, and micromolecular polyhydric alcohol connects the arms in a core form, and this synthesis mode also contains rigid diisocyanate structure in the arms of soft segment, so that the phase separation effect of soft segment and hard segment is not obvious, high elasticity and high strength are difficult to realize, and impact and abrasion of external force are easy to be applied. It has been reported in the prior art that it is difficult to obtain a room temperature curable coating which is solvent-free, low in energy consumption, good in abrasion resistance and excellent in hydrophilic property.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides photo-thermal dual-curing resin which is of a hyperbranched structure, has double bonds on the surface for photo-curing and hydroxyl groups on the surface for thermal curing, and has the advantages of low viscosity, high thermoplasticity, high elasticity and good wear resistance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of hydrophilic wear-resistant photo-thermal dual-curing resin, which comprises the following steps:
1) Reacting a diisocyanate with a small molecule polyol to obtain a branched NCO-terminated prepolymer 1, wherein the molar ratio of isocyanate groups (-NCO) of the diisocyanate to hydroxyl groups (-OH) of the small molecule polyol is 2:1;
2) The prepolymer 1 reacts with dihydric alcohol to form hyperbranched resin, wherein the molar ratio of isocyanate groups (-NCO) of the prepolymer 1 to hydroxyl groups (-OH) of the dihydric alcohol is between 1:1 and 1:2;
3) The hydroxy acrylate monomer and diisocyanate are mixed according to the molar ratio of hydroxyl (-OH) to isocyanate (-NCO) of 1:1 to obtain a partially end-capped prepolymer 2;
4) The hyperbranched resin obtained in the step 2) and the prepolymer 2 obtained in the step 3) are mixed according to a molar ratio of hydroxyl (-OH) to isocyanate (-NCO) of 4:1-1:1, mixing and reacting to obtain the photo-thermal dual-curing resin.
Preferably, the diisocyanate comprises one or a combination of at least two of isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), modified diphenylmethane diisocyanate (liquefied MDI);
the small molecular polyalcohol comprises at least one of pentaerythritol, glycerol, trimethylolpropane and trimethylolethane;
the dihydric alcohol comprises at least one of 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol, 1, 6-hexanediol, dimethylolpropionic acid, dimethylolbutyric acid and polyethylene glycol (molecular weight 200-1000);
the hydroxy acrylate monomer comprises at least one of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 4-hydroxy butyl acrylate (4 HBA) and pentaerythritol triacrylate (PETA).
In the technical scheme, dibutyl tin dilaurate (DBTDL) is additionally added as a catalyst, p-hydroxyanisole (MEHQ) as a polymerization inhibitor and 2, 6-di-tert-butyl-4-methylphenol (BHT) as an antioxidant in the process of preparing the hydrophilic wear-resistant photo-thermal dual-curing resin; the catalyst accounts for 0.01 to 0.05 percent of the mass of the resin, the polymerization inhibitor accounts for 0.01 to 0.05 percent of the mass of the prepolymer 2, and the antioxidant accounts for 0.05 to 0.1 percent.
In the preparation method of the hydrophilic wear-resistant photo-thermal dual-curing resin, specifically, in the step 1), diisocyanate and dibutyltin dilaurate are firstly added into a reaction kettle, and stirring and mixing are carried out uniformly; and fully mixing the micromolecular polyalcohol with a solvent until the micromolecular polyalcohol is completely dissolved, transferring the mixture into a constant-pressure dropping liquid tank, slowly dropping the mixture into the reaction kettle at room temperature, continuously reacting at room temperature for 30min, and heating the mixture to 60-70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value to obtain a prepolymer 1, wherein the solvent is one or more of absolute ethyl alcohol, isopropanol, ethyl acetate, butyl acetate, toluene, xylene, acetone, butanone, cyclohexanone, N-butyl ether and N-methylpyrrolidone.
Specifically, in the step 2), dihydric alcohol is added into the prepolymer 1, and the reaction is continued at the temperature of 60-70 ℃ until the content of isocyanate groups (-NCO) is zero, so as to obtain the hyperbranched resin.
Specifically, in the step 3), a reaction kettle is used, diisocyanate and dibutyltin dilaurate are added into the reaction kettle, and stirring is started; and sequentially weighing p-hydroxyanisole, 2, 6-di-tert-butyl-4-methylphenol and hydroxyacrylate monomers, fully mixing until the monomers are completely dissolved, transferring the mixture into a constant pressure dropping tank, slowly dropping the mixture into a reaction kettle at room temperature, continuously reacting for 30min at room temperature, heating the mixture to 60-70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), and cooling the mixture to obtain the prepolymer 2.
Specifically, step 4) adding the prepolymer 2 into hyperbranched resin, continuing to react at 60-70 ℃ until the content of isocyanate groups (-NCO) is zero, obtaining the photo-thermal dual-cured resin, distilling under reduced pressure to remove the solvent, drying, sealing and preserving.
Compared with the prior art, the invention has the following outstanding effects:
the invention designs a hydrophilic polymer with photo-thermal dual curing function, which adopts a synthesis mode of 'first nucleus and then arm', diisocyanate reacts with micromolecular polyol to form nucleus firstly, dihydric alcohol directly connects the nuclei in an arm mode, the synthesis mode is easier to obtain hyperbranched structure, the nucleus is equivalent to a hard segment, the arm is equivalent to a soft segment, and a structure similar to a thermoplastic elastomer can be formed, so that the hydrophilic polymer has high elasticity and high strength, and can resist impact and abrasion of external force. In addition, the hydrophilic chain segment can exert hydrophilic performance for a long time, the water contact angle is maintained within 5 ℃ for a long time, and the hyperbranched structure of the hydrophilic chain segment ensures that the molecular chain is not easy to tangle, has smaller viscosity and good solubility. Is suitable for preparing solvent-free, safe and nontoxic, high-strength and wear-resistant super-hydrophilic coating. The coating can form a film on various types of substrates, can realize instant solidification under ultraviolet light, can be applied to continuous industrial production, has high bonding strength between the formed coating and the substrates, has good transparency, high hardness, scratch resistance and chemical resistance, and has excellent hydrophilic effect, good water resistance and low viscosity.
Drawings
FIG. 1 is a schematic representation of the core-before-arm synthesis of hyperbranched resins of examples 1-4;
FIG. 2 is a schematic representation of the arm-first and core-last synthesis of a hyperbranched resin of comparative example.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
In the process of preparing the photo-thermal dual-curing resin, dibutyl tin dilaurate DBTDL, p-hydroxyanisole MEHQ and 2, 6-di-tert-butyl-4-methylphenol BHT are additionally added, so that the photo-thermal dual-curing resin is a conventional choice, has no influence on performance, and plays roles of a catalyst and a polymerization inhibitor.
Example 1
Step 1) to the reaction vessel, 444.6g (2.0 mol) of isophorone diisocyanate and 0.9g (0.1 wt%) of dibutyltin dilaurate were added and stirring was started; mixing and dissolving 134.1g (1.0 mol) of trimethylolpropane with 500g of isopropanol and 1000g of ethyl acetate, transferring to a constant-pressure dropping tank, slowly dropping into the reaction kettle at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), continuing to react at room temperature for 30min after dropping, and heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), so as to obtain a hydrophilically modified prepolymer 1;
step 2) then adding 23.6g (0.2 mol) of 1, 6-hexanediol and 400g (1.0 mol) of polyethylene glycol 400, and continuing the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining hyperbranched resin;
step 3) in another reaction vessel, 111.1g (0.5 mol) isophorone diisocyanate and 0.16g (0.1 wt%) dibutyltin dilaurate were added and stirring was started; and sequentially weighing 0.44g (0.262 wt%) of p-hydroxyanisole, 0.88g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 58g (0.5 mol) of hydroxyethyl acrylate, fully mixing until the materials are completely dissolved, transferring the materials into a constant-pressure dropping tank, slowly dropping the materials into a reaction kettle in the last step at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), after the reaction at room temperature is continuously carried out for 30min, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining the photo-thermal dual-cured resin, removing the solvent by reduced pressure distillation, drying, sealing and preserving.
Example 2
Step 1) 348.3g (2.0 mol) toluene diisocyanate and 0.8g (0.1 wt%) dibutyltin dilaurate were added to the reaction vessel with stirring; mixing and dissolving 92g (1.0 mol) of glycerin with 1500g of butyl acetate, fully mixing until the glycerin is completely dissolved, transferring the mixture into a constant-pressure dropping liquid tank, slowly dropping the mixture into the reaction kettle at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), continuously reacting at room temperature for 30min after dropping, and heating the mixture to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), so as to obtain a hydrophilically modified prepolymer 1;
step 2) then adding 27g (0.3 mol) of 1, 4-butanediol and 840g (1.4 mol) of polyethylene glycol 600, and continuing to react until the content of isocyanate groups (-NCO) is zero, so as to obtain hyperbranched resin;
step 3) in another reaction vessel, 111.1g (0.5 mol) of isophorone diisocyanate and 0.26g (0.1 wt%) of dibutyltin dilaurate were added and stirring was started; and sequentially weighing 0.68g (0.262 wt%) of p-hydroxyanisole, 1.36g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 149g (0.5 mol) of pentaerythritol triacrylate, fully mixing to be completely dissolved, transferring into a constant-pressure dropping tank, slowly dropping into the reaction kettle in the last step at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), after the reaction at room temperature is continuously carried out for 30min, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining the photo-thermal dual-cured resin, removing the solvent by reduced pressure distillation, drying, sealing and preserving.
Example 3
Step 1) 348.3g (2.0 mol) toluene diisocyanate and 0.8g (0.1 wt%) dibutyltin dilaurate were added to the reaction vessel with stirring; mixing and dissolving 134g (1.0 mol) of trimethylolpropane with 1000g of toluene and 1000g of isopropanol, fully mixing until the trimethylolpropane is completely dissolved, transferring the mixture into a constant-pressure dropping liquid tank, slowly dropping the mixture into the reaction kettle at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), continuously reacting for 30min at room temperature after dropping, and heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), thereby obtaining a hydrophilically modified prepolymer 1;
step 2) then adding 27g (0.3 mol) of 1, 4-butanediol and 600g (1.0 mol) of polyethylene glycol 600, and continuing the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining hyperbranched resin;
step 3) 67.2g (0.4 mol) of hexamethylene diisocyanate and 0.12g (0.1 wt%) of dibutyltin dilaurate were added to another reactor with stirring; and sequentially weighing 0.3g (0.262 wt%) of p-hydroxyanisole, 0.6g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 52.0g (0.4 mol) of hydroxypropyl acrylate (HPA), fully mixing until the materials are completely dissolved, transferring the materials into a constant-pressure dropping tank, slowly dropping the materials into a reaction kettle in the last step at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), after the reaction at room temperature is continuously carried out for 30min, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining the photo-thermal dual-cured resin, removing the solvent by reduced pressure distillation, drying, sealing and preserving.
Example 4
Step 1) to the reaction vessel, 444.6g (2.0 mol) of isophorone diisocyanate and 0.9g (0.1 wt%) of dibutyltin dilaurate were added and stirring was started; mixing and dissolving 120g (1.0 mol) of trimethylolethane with 1000g of absolute ethyl alcohol and 1000g of isopropanol, fully mixing until the trimethylolethane is completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into the reaction kettle at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), continuing to react at room temperature for 30min after dropping, and heating the mixture to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), thus obtaining a hydrophilically modified prepolymer 1;
step 2) then adding 23.6g (0.2 mol) of 1, 6-hexanediol and 480g (1.2 mol) of polyethylene glycol 400, and continuing the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining hyperbranched resin;
step 3) in another reaction vessel, 222.2g (1.0 mol) isophorone diisocyanate and 0.36g (0.1 wt%) dibutyltin dilaurate were added and stirring was started; and sequentially weighing 0.94g (0.262 wt%) of p-hydroxyanisole, 1.88g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 144g (1.0 mol) of 4-hydroxybutyl acrylate (4 HBA), fully mixing until the materials are completely dissolved, transferring the materials into a constant pressure dropping tank, slowly dropping the materials into a reaction kettle in the last step at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), continuously reacting at room temperature for 30min after the dropping is finished, heating to 70 ℃ for reacting until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining the photo-thermal dual-cured resin, removing the solvent by reduced pressure distillation, drying, sealing and preserving.
Comparative examples
Step 1) to the reaction vessel, 444.6g (2.0 mol) of isophorone diisocyanate and 0.9g (0.1 wt%) of dibutyltin dilaurate were added and stirring was started; weighing 23.6g (0.2 mol) of 1, 6-hexanediol and 320g (0.8 mol) of polyethylene glycol 400, fully mixing until the materials are completely dissolved, transferring the materials into a constant pressure dropping tank, slowly dropping the materials into the reaction kettle at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), continuously reacting at room temperature for 30min after dropping, and heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), so as to obtain a hydrophilically modified prepolymer 1;
step 2) adding 268.3g (2.0 mol) of trimethylolpropane to continuously react until the content of isocyanate groups (-NCO) is zero, so as to obtain hyperbranched resin;
step 3) in another reaction vessel, 111.1g (0.5 mol) isophorone diisocyanate and 0.16g (0.1 wt%) dibutyltin dilaurate were added and stirring was started; and sequentially weighing 0.44g (0.262 wt%) of p-hydroxyanisole, 0.88g (0.525 wt%) of 2, 6-di-tert-butyl-4-methylphenol and 58g (0.5 mol) of hydroxyethyl acrylate, fully mixing until the materials are completely dissolved, transferring the materials into a constant-pressure dropping tank, slowly dropping the materials into a reaction kettle in the last step at room temperature (the reaction is violently exothermic, the dropping speed is controlled to avoid local overheating), after the reaction at room temperature is continuously carried out for 30min, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (measured by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue the reaction until the content of isocyanate groups (-NCO) is zero, thus obtaining the photo-thermal dual-cured resin, removing the solvent by reduced pressure distillation, drying, sealing and preserving.
Performance testing
The photo-thermal dual-curing hyperbranched resins prepared in examples 1 to 4 and comparative example were uniformly mixed with a photoinitiator 1173 and an isocyanate curing agent Desmodur N3390 in a mass ratio of 95:5:10, then uniformly coated on a clean PET film with a wire rod, then placed on a conveyor type UV curing machine, cured by 800mJ ultraviolet light, and then placed under room temperature for 7d to test performance.
Table 1 items and methods for testing the performance of superhydrophilic coatings prepared in examples 1-4 and comparative example
TABLE 2 results of Performance test of superhydrophilic coatings prepared in examples 1-4 and comparative example
As shown in fig. 1 and 2, the hydrophilic polymer with photo-thermal dual curing function designed in examples 1-4 adopts a synthesis mode of 'first nucleus and then arm', diisocyanate reacts with small molecular polyol to form nucleus first, dihydric alcohol directly connects the nuclei in the form of arm, and compared with a synthesis mode of first arm and then nucleus (namely, react with dihydric alcohol to form arm and then react with small molecular polyol to form nucleus) in comparative example, the synthesis mode is easier to obtain hyperbranched structure, the nucleus is equivalent to hard segment, the arm is equivalent to soft segment, and a structure similar to thermoplastic elastomer can be formed, thus the hydrophilic polymer has high elasticity and high strength, and can resist impact and abrasion of external force. Thus, the pencil hardness is higher and more scratch and alcohol rub resistant than the comparative example.
Claims (8)
1. The preparation method of the hydrophilic wear-resistant photo-thermal dual-curing resin is characterized by comprising the following steps of:
1) Reacting a diisocyanate with a small molecule polyol to obtain a branched NCO-terminated prepolymer 1, wherein the molar ratio of isocyanate groups (-NCO) of the diisocyanate to hydroxyl groups (-OH) of the small molecule polyol is 2:1;
2) The prepolymer 1 reacts with dihydric alcohol to form hyperbranched resin, wherein the molar ratio of isocyanate groups (-NCO) of the prepolymer 1 to hydroxyl groups (-OH) of the dihydric alcohol is between 1:1 and 1:2;
3) The hydroxy acrylate monomer and diisocyanate are mixed according to the molar ratio of hydroxyl (-OH) to isocyanate (-NCO) of 1:1 to obtain a partially end-capped prepolymer 2;
4) The hyperbranched resin obtained in the step 2) and the prepolymer 2 obtained in the step 3) are mixed according to a molar ratio of hydroxyl (-OH) to isocyanate (-NCO) of 4:1, mixing and reacting to obtain photo-thermal dual-curing resin;
the dihydric alcohol is a mixture of one of 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol and 1, 6-hexanediol and polyethylene glycol with the molecular weight of 200-1000;
the diisocyanate comprises one or a combination of at least two of isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) and modified diphenylmethane diisocyanate (liquefied MDI).
2. The method for preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 1, wherein the method comprises the following steps: the small molecule polyol comprises at least one of pentaerythritol, glycerol, trimethylolpropane and trimethylolethane.
3. The method for preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 1, wherein the method comprises the following steps: the hydroxy acrylate monomer comprises at least one of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 4-hydroxy butyl acrylate (4 HBA) and pentaerythritol triacrylate (PETA).
4. The method for preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 1, wherein dibutyltin dilaurate (DBTDL) is additionally added as a catalyst, p-hydroxyanisole (MEHQ) is used as a polymerization inhibitor, and 2, 6-di-tert-butyl-4-methylphenol (BHT) is used as an antioxidant in the process of preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin; the catalyst accounts for 0.01 to 0.05 percent of the mass of the resin, and the polymerization inhibitor accounts for 0.01 to 0.05 percent of the prepolymer 2.
5. The method for preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 4, wherein in the step 1), diisocyanate and dibutyltin dilaurate are added into a reaction kettle, and stirring and mixing are carried out uniformly; and fully mixing the micromolecular polyalcohol with a solvent until the micromolecular polyalcohol is completely dissolved, transferring the mixture into a constant-pressure dropping liquid tank, slowly dropping the mixture into the reaction kettle at room temperature, continuously reacting at room temperature for 30min, and heating the mixture to 60-70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value to obtain a prepolymer 1, wherein the solvent is one or more of absolute ethyl alcohol, isopropanol, ethyl acetate, butyl acetate, toluene, xylene, acetone, butanone, cyclohexanone and n-butyl ether.
6. The method for preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 1, wherein in the step 2), dihydric alcohol is added into the prepolymer 1, and the reaction is continued at 60-70 ℃ until the content of isocyanate groups (-NCO) is zero, so as to obtain the hyperbranched resin.
7. The method for preparing a hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 5, wherein in the step 3), a reaction kettle is used, diisocyanate and dibutyltin dilaurate are added into the reaction kettle, and stirring is started; and sequentially weighing p-hydroxyanisole, 2, 6-di-tert-butyl-4-methylphenol and hydroxyacrylate monomers, fully mixing until the monomers are completely dissolved, transferring the mixture into a constant pressure dropping tank, slowly dropping the mixture into a reaction kettle at room temperature, continuously reacting at room temperature for 30min, heating the mixture to 60-70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value, wherein the theoretical value is measured by a di-n-butylamine hydrochloride method, and cooling the mixture to obtain the prepolymer 2.
8. The method for preparing the hydrophilic abrasion-resistant photo-thermal dual-curing resin according to claim 1, wherein in the step 4), the prepolymer 2 is added into the hyperbranched resin to continue to react at 60-70 ℃ until the content of isocyanate groups (-NCO) is zero, so as to obtain the photo-thermal dual-curing resin, the solvent is removed by reduced pressure distillation, and the resin is dried, sealed and stored.
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