CN114085353A - Light-heat dual-curing resin and preparation method thereof - Google Patents
Light-heat 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 a light-heat dual-curing resin and a preparation method thereof. The invention adopts a synthesis mode of 'first nucleus and second arm', diisocyanate reacts with micromolecular polyol to form a nucleus firstly, and diol directly connects the nuclei in the form of arms, so that the synthesis mode is easier to obtain a hyperbranched structure, the nucleus is equivalent to a hard segment, and the arms are 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 the impact and abrasion of external force.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a light-heat dual-curing resin and a preparation method thereof.
Background
The super-hydrophilic surface has strong interaction force with water, water drops are dripped on the super-hydrophilic surface and can be completely spread in a short time, so that the contact angle is equal to or close to 0 degree, and the super-hydrophilic surface has very wide application prospects in the fields of self-cleaning, flow guiding, pollution prevention, biological consumables and the like, and is one of the hot spots of current research. The methods for realizing the super-hydrophilicity are chemical modification methods (such as plasma treatment) or surface coating methods, but both the chemical modification methods have some problems, expensive instruments and equipment or complex process flows are required to be adopted in the chemical modification methods, the chemical modification methods are easily influenced by external conditions (such as light, heat, oxygen and the like), and the application fields still need to be developed. The surface coating method relies on a hydrophilic surfactant for the first time to provide hydrophilic properties, is less durable, is easily deteriorated by water, and is gradually replaced with a hydrophilic resin. There are thermosetting type hydrophilic resins and UV (ultraviolet) photo-curable type hydrophilic resins, depending on the curing method. Although the heat-curable hydrophilic resins can provide good abrasion resistance, they require long curing time and high energy consumption for solvent evaporation, and are inefficient in production. The UV (ultraviolet) light-curing type hydrophilic resin generally has higher light transmittance than a heat-curing type hydrophilic resin, can realize instant curing under ultraviolet light, is very suitable for continuous industrial production, but the wear resistance of the UV (ultraviolet) light-curing type hydrophilic resin is usually lower than that of a heat-curing coating.
In order to overcome the problems, many researchers provide a light-heat dual-curing mode, and the convenience of light curing and the good wear resistance of heat curing are combined together to exert respective advantages. CN104087137 mixed UV resin and inorganic siloxane realize the photo-curing and thermosetting functions respectively, the photo-curing and thermosetting functions are realized by single curing function resin respectively, the photo-curing resin and the thermosetting resin are only physically connected without forming chemical bonds, and the performance superposition effect is not obvious. CN107400407 adopts a synthesis mode of 'arm first and core last', diisocyanate reacts with dihydric alcohol first to form an arm, and micromolecular polyol connects the arms in a core form, and the synthesis mode has an unobvious phase separation effect of soft and hard segments because the arms of the soft segments also contain rigid diisocyanate structures, so that high elasticity and high strength are difficult to realize, and the soft segments are easy to be impacted and abraded by external force. The existing reports show that the room temperature curing coating which has no solvent, low energy consumption, good wear resistance and excellent hydrophilic performance is difficult to obtain.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a photo-thermal dual-curing resin which is a hyperbranched structure, has double bonds on the surface for photo-curing and hydroxyl groups for thermal curing, and has low viscosity, high thermoplasticity, high elasticity and good wear resistance.
In order to achieve the 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 diisocyanate with micromolecular 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 micromolecular polyol is 2: 1;
2) the prepolymer 1 reacts with dihydric alcohol to form hyperbranched resin, wherein the molar ratio of isocyanate (-NCO) of the prepolymer 1 to hydroxyl (-OH) of the dihydric alcohol is 1:1-1: 2;
3) mixing a hydroxyl acrylate monomer and diisocyanate according to a molar ratio of hydroxyl (-OH) to isocyanate (-NCO) of 1:1, obtaining a prepolymer 2 with a partially terminated end;
4) mixing the hyperbranched resin obtained in the step 2) and the prepolymer 2 obtained in the step 3) 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 polyol 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-;
the hydroxyl acrylate monomer comprises at least one of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4HBA) and pentaerythritol triacrylate (PETA).
In the process of preparing the hydrophilic wear-resistant photo-thermal dual-curing resin, dibutyltin dilaurate (DBTDL) serving as a catalyst, p-hydroxyanisole (MEHQ) serving as a polymerization inhibitor and 2, 6-di-tert-butyl-4-methylphenol (BHT) serving as an antioxidant are additionally added; the catalyst accounts for 0.01-0.05 percent of the mass of the resin, the polymerization inhibitor accounts for 0.01-0.05 percent of the prepolymer 2, and the antioxidant accounts for 0.05-0.1 percent.
In the preparation method of the hydrophilic wear-resistant photo-thermal dual-curing resin, in the step 1), diisocyanate and dibutyltin dilaurate are added into a reaction kettle firstly, and are started, stirred and mixed uniformly; and fully mixing the micromolecule polyhydric alcohol with a solvent until the micromolecule polyhydric alcohol is completely dissolved, transferring the micromolecule polyhydric alcohol into a constant-pressure liquid dropping tank, slowly dropping the micromolecule polyhydric alcohol into the reaction kettle at room temperature, continuing to react at room temperature for 30min, and heating to 60-70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value to obtain the prepolymer 1, wherein the solvent is one or more of absolute ethyl alcohol, isopropanol, ethyl acetate, butyl acetate, methylbenzene, dimethylbenzene, 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 group (-NCO) is zero, so as to obtain the hyperbranched resin.
Specifically, adding diisocyanate and dibutyltin dilaurate into a reaction kettle in the step 3), starting stirring; and weighing p-hydroxyanisole, 2, 6-di-tert-butyl-4-methylphenol and a hydroxyl acrylate monomer in sequence, fully mixing until the p-hydroxyanisole, the 2, 6-di-tert-butyl-4-methylphenol and the hydroxyl acrylate monomer are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into a reaction kettle at room temperature, continuing to react at room temperature for 30min after dropping, heating to 60-70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2.
Specifically, 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 group (-NCO) is zero, so as to obtain the photo-thermal dual-curing resin, and the photo-thermal dual-curing resin is subjected to reduced pressure distillation to remove the solvent, drying, sealing and storing.
Compared with the prior art, the invention has the following outstanding effects:
the invention designs a hydrophilic polymer with light-heat dual curing function, which adopts a synthesis mode of 'nucleus first and arm later', diisocyanate reacts with micromolecular polyol to form nucleus first, and the diol directly connects the nucleus in the form of arm. In addition, the hydrophilic chain segment can exert the hydrophilic performance for a long time, the water contact angle is maintained within 5 degrees for a long time, and the hyperbranched structure of the modified polyvinyl acetal resin enables molecular chains to be difficult to tangle, and has low viscosity and good solubility. Is suitable for preparing solvent-free, safe, nontoxic, high-strength and wear-resistant super-hydrophilic coating. The coating can form a film on various types of base materials, can realize instant curing under ultraviolet light, can be applied to continuous industrial production, and has high bonding strength with the base materials, good transparency, high hardness, scratch resistance and chemical resistance, excellent hydrophilic effect, good water resistance and low viscosity.
Drawings
FIG. 1 is a schematic illustration of core-first arm synthesis of hyperbranched resins of examples 1-4;
FIG. 2 is a schematic diagram of a first arm then core synthesis of a hyperbranched resin of a 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 invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
During the preparation of the photo-thermal dual-curing resin, dibutyltin dilaurate DBTDL, p-hydroxyanisole MEHQ and 2, 6-di-tert-butyl-4-methylphenol BHT are additionally added, which is a conventional choice, has no influence on the performance, and plays the roles of a catalyst and a polymerization inhibitor.
Example 1
Step 1) adding 444.6g (2.0mol) of isophorone diisocyanate and 0.9g (0.1wt%) of dibutyltin dilaurate into a reaction kettle, and starting stirring; mixing and dissolving 134.1g (1.0mol) of trimethylolpropane by using 500g of isopropanol and 1000g of ethyl acetate, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into the reaction kettle at room temperature (the reaction is violent in heat release, and the dropping speed is controlled to avoid local overheating), continuing reacting at room temperature for 30min after dropping, and heating to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), thus obtaining a hydrophilic modified prepolymer 1;
step 2) adding 23.6g (0.2mol) of 1, 6-hexanediol and 400g (1.0mol) of polyethylene glycol 400, and continuing to react until the content of isocyanate group (-NCO) is zero to obtain hyperbranched resin;
step 3) adding 111.1g (0.5mol) of isophorone diisocyanate and 0.16g (0.1wt%) of dibutyltin dilaurate into another reaction kettle, and starting stirring; weighing 0.44g (0.262 wt%) of p-hydroxyanisole, 0.88g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 58g (0.5mol) of hydroxyethyl acrylate in sequence, fully mixing until the p-hydroxyanisole, the 2, 6-di-tert-butyl-4-methylphenol and the 58g (0.5mol) of hydroxyethyl acrylate are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into the reaction kettle in the last step at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), continuing to react at room temperature for 30min after the dropping is finished, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and cooling to obtain prepolymer 2;
and 4) adding the hyperbranched resin to continue reacting until the content of isocyanate group (-NCO) is zero to obtain light-heat dual-curing resin, distilling under reduced pressure to remove the solvent, drying, sealing and storing.
Example 2
Step 1) 348.3g (2.0mol) of toluene diisocyanate and 0.8g (0.1wt%) of dibutyltin dilaurate were added to a reaction kettle and stirred; dissolving 92g (1.0mol) of glycerol in 1500g of butyl acetate, fully mixing until the glycerol 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 violent in heat release, and the dropping speed is controlled to avoid local overheating), continuing reacting at room temperature for 30min after dropping, and heating to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), thus obtaining a hydrophilic modified prepolymer 1;
step 2) 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 group (-NCO) is zero to obtain hyperbranched resin;
step 3) adding 111.1g (0.5mol) of isophorone diisocyanate and 0.26g (0.1wt%) of dibutyltin dilaurate into another reaction kettle, and starting stirring; weighing 0.68g (0.262 wt%) of p-hydroxyanisole, 1.36g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 149g (0.5mol) of pentaerythritol triacrylate in sequence, fully mixing until the p-hydroxyanisole, 1.36g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 149g (0.5mol) of pentaerythritol triacrylate are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into the reaction kettle in the last step at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), after dropping, continuing to react at room temperature for 30min, heating to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and cooling to obtain prepolymer 2;
and 4) adding the hyperbranched resin to continue reacting until the content of isocyanate group (-NCO) is zero to obtain light-heat dual-curing resin, distilling under reduced pressure to remove the solvent, drying, sealing and storing.
Example 3
Step 1) 348.3g (2.0mol) of toluene diisocyanate and 0.8g (0.1wt%) of dibutyltin dilaurate were added to a reaction kettle and stirred; mixing and dissolving 134g (1.0mol) of trimethylolpropane by using 1000g of toluene and 1000g of isopropanol, fully mixing until the trimethylolpropane 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 violent in heat release, and the dropping speed is controlled to avoid local overheating), continuing reacting at room temperature for 30min after dropping, and heating to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), thus obtaining a hydrophilic modified prepolymer 1;
step 2) adding 27g (0.3 mol) of 1, 4-butanediol and 600g (1.0mol) of polyethylene glycol 600, and continuing to react until the content of isocyanate group (-NCO) is zero to obtain hyperbranched resin;
step 3) in another reactor, 67.2g (0.4mol) of hexamethylene diisocyanate and 0.12g (0.1wt%) of dibutyltin dilaurate were added and stirring was started; weighing 0.3g (0.262 wt%) of p-hydroxyanisole, 0.6g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 52.0g (0.4mol) of hydroxypropyl acrylate (HPA) in sequence, fully mixing until the p-hydroxyanisole, the 0.6g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and the 52.0g (0.4mol) of hydroxypropyl acrylate are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into a reaction kettle in the last step at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), after dropping, continuing to react at room temperature for 30min, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue reacting until the content of isocyanate group (-NCO) is zero to obtain light-heat dual-curing resin, distilling under reduced pressure to remove the solvent, drying, sealing and storing.
Example 4
Step 1) adding 444.6g (2.0mol) of isophorone diisocyanate and 0.9g (0.1wt%) of dibutyltin dilaurate into a reaction kettle, and starting stirring; mixing and dissolving 120g (1.0mol) of trimethylolethane by using 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 violent in heat release, and the dropping speed is controlled to avoid local overheating), after dropping, continuing to react at room temperature for 30min, heating to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and obtaining a hydrophilic modified prepolymer 1;
step 2) adding 23.6g (0.2mol) of 1, 6-hexanediol and 480g (1.2 mol) of polyethylene glycol 400, and continuing to react until the content of isocyanate group (-NCO) is zero to obtain hyperbranched resin;
step 3) adding 222.2g (1.0mol) of isophorone diisocyanate and 0.36g (0.1wt%) of dibutyltin dilaurate into another reaction kettle, and starting stirring; weighing 0.94g (0.262 wt%) of p-hydroxyanisole, 1.88g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 144g (1.0mol) of 4-hydroxybutylacrylate (4HBA) in sequence, fully mixing until the p-hydroxyanisole, 1.88g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 144g (1.0mol) of 4-hydroxybutylacrylate (4HBA) are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into a reaction kettle in the previous step at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), after dropping, continuing to react at room temperature for 30min, heating to 70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value (determined by a n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2;
and 4) adding the hyperbranched resin to continue reacting until the content of isocyanate group (-NCO) is zero to obtain light-heat dual-curing resin, distilling under reduced pressure to remove the solvent, drying, sealing and storing.
Comparative examples
Step 1) adding 444.6g (2.0mol) of isophorone diisocyanate and 0.9g (0.1wt%) of dibutyltin dilaurate into a reaction kettle, and starting stirring; weighing 23.6g (0.2mol) of 1, 6-hexanediol and 320g (0.8mol) of polyethylene glycol 400, fully mixing until the mixture is completely dissolved, transferring the mixture to a constant-pressure dropping tank, slowly dropping the mixture into the reaction kettle at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), continuing the reaction at room temperature for 30min after the dropping is finished, and heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), thus obtaining a hydrophilic modified prepolymer 1;
step 2) adding 268.3g (2.0mol) of trimethylolpropane to continue the reaction until the content of isocyanate group (-NCO) is zero, and obtaining hyperbranched resin;
step 3) adding 111.1g (0.5mol) of isophorone diisocyanate and 0.16g (0.1wt%) of dibutyltin dilaurate into another reaction kettle, and starting stirring; weighing 0.44g (0.262 wt%) of p-hydroxyanisole, 0.88g (0.525wt%) of 2, 6-di-tert-butyl-4-methylphenol and 58g (0.5mol) of hydroxyethyl acrylate in sequence, fully mixing until the p-hydroxyanisole, the 2, 6-di-tert-butyl-4-methylphenol and the 58g (0.5mol) of hydroxyethyl acrylate are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into the reaction kettle in the last step at room temperature (the reaction is violent in heat release, the dropping speed is controlled to avoid local overheating), continuing to react at room temperature for 30min after the dropping is finished, heating to 70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and cooling to obtain prepolymer 2;
and 4) adding the hyperbranched resin to continue reacting until the content of isocyanate group (-NCO) is zero to obtain light-heat dual-curing resin, distilling under reduced pressure to remove the solvent, drying, sealing and storing.
Performance testing
The photo-thermal dual-curing hyperbranched resin prepared in the examples 1 to 4 and the comparative example is uniformly mixed with the photoinitiator 1173 and the isocyanate curing agent Desmodur N3390 according to the mass ratio of 95:5:10, then the mixture is uniformly coated on a clean PET film by a wire bar, and then the clean PET film is placed on a conveyor belt type UV curing machine, is cured by 800mJ ultraviolet light, and is placed at room temperature for 7d to test the performance.
TABLE 1 PERFORMANCE TEST PROCEDURE AND METHOD FOR PERIOPHILIC COATINGS OBTAINED IN EXAMPLES 1-4 AND COMPARATIVE EXAMPLES
TABLE 2 results of performance testing of the super hydrophilic coatings obtained in examples 1-4 and comparative examples
As shown in FIGS. 1 and 2, the photo-thermal dual-curing hydrophilic polymer designed in examples 1-4 adopts a "core-first-arm" synthesis method, wherein diisocyanate reacts with small-molecule polyol to form core, and diol directly connects the core in an arm form, compared with the comparative example which adopts a "core-first-arm" synthesis method (i.e., reacts with diol to form arm, and then reacts with small-molecule polyol to form core), the synthesis method is easier to obtain hyperbranched structure, and the core 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, so that the polymer has high elasticity and high strength, and can resist impact and abrasion of external force. Thus, the pencil hardness was higher, and it was more resistant to scratching and alcohol rubbing than the comparative examples.
Claims (10)
1. A preparation method of hydrophilic wear-resistant photo-thermal dual-curing resin is characterized by comprising the following steps:
1) reacting diisocyanate with micromolecular 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 micromolecular polyol is 2: 1;
2) the prepolymer 1 reacts with dihydric alcohol to form hyperbranched resin, wherein the molar ratio of isocyanate (-NCO) of the prepolymer 1 to hydroxyl (-OH) of the dihydric alcohol is 1:1-1: 2;
3) mixing a hydroxyl acrylate monomer and diisocyanate according to a molar ratio of hydroxyl (-OH) to isocyanate (-NCO) of 1:1, obtaining a prepolymer 2 with a partially terminated end;
4) mixing the hyperbranched resin obtained in the step 2) and the prepolymer 2 obtained in the step 3) 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.
2. The method for preparing the hydrophilic wear-resistant photo-thermal dual-curable resin according to claim 1, wherein: the diisocyanate comprises one or a combination of at least two of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI) and modified diphenyl methane diisocyanate (liquefied MDI).
3. The method for preparing the hydrophilic wear-resistant photo-thermal dual-curable resin according to claim 1, wherein: the small molecule polyol comprises at least one of pentaerythritol, glycerol, trimethylolpropane and trimethylolethane.
4. The method for preparing the hydrophilic wear-resistant photo-thermal dual-curable resin according to claim 1, wherein: the dihydric alcohol comprises at least one of 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-pentanediol, 1, 6-hexanediol and polyethylene glycol (molecular weight 200-.
5. The method for preparing the hydrophilic wear-resistant photo-thermal dual-curable resin according to claim 1, wherein: the hydroxyl acrylate monomer comprises at least one of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4HBA) and pentaerythritol triacrylate (PETA).
6. The method for preparing the hydrophilic wear-resistant photo-thermal dual-cured resin according to claim 1, wherein additionally dibutyltin dilaurate (DBTDL) is added as a catalyst, p-hydroxyanisole (MEHQ) is added as a polymerization inhibitor, and 2, 6-di-tert-butyl-4-methylphenol (BHT) is added as an antioxidant in the process of preparing the hydrophilic wear-resistant photo-thermal dual-cured resin; the catalyst accounts for 0.01-0.05 percent of the mass of the resin, the polymerization inhibitor accounts for 0.01-0.05 percent of the prepolymer 2, and the antioxidant accounts for 0.05-0.1 percent.
7. The preparation method of the hydrophilic wear-resistant photo-thermal dual-curing resin as claimed in claim 6, wherein in the step 1), the diisocyanate and the dibutyltin dilaurate are added into a reaction kettle and uniformly mixed by stirring; and fully mixing the micromolecule polyhydric alcohol with a solvent until the micromolecule polyhydric alcohol is completely dissolved, transferring the micromolecule polyhydric alcohol into a constant-pressure liquid dropping tank, slowly dropping the micromolecule polyhydric alcohol into the reaction kettle at room temperature, continuing to react at room temperature for 30min, and heating to 60-70 ℃ for reaction until the content of isocyanate group (-NCO) of the mixture reaches a theoretical value to obtain the prepolymer 1, wherein the solvent is one or more of absolute ethyl alcohol, isopropanol, ethyl acetate, butyl acetate, methylbenzene, dimethylbenzene, acetone, butanone, cyclohexanone and n-butyl ether.
8. The preparation method of the hydrophilic wear-resistant photo-thermal dual-curing resin as claimed in claim 1, wherein step 2) is to add the dihydric alcohol into the prepolymer 1, and keep the temperature at 60-70 ℃ to continue the reaction until the content of the isocyanate group (-NCO) is zero, so as to obtain the hyperbranched resin.
9. The method for preparing the hydrophilic wear-resistant photo-thermal dual-curing resin according to claim 6, wherein a reaction kettle is used in the step 3), diisocyanate and dibutyltin dilaurate are added to the reaction kettle, and stirring is started; and weighing p-hydroxyanisole, 2, 6-di-tert-butyl-4-methylphenol and a hydroxyl acrylate monomer in sequence, fully mixing until the p-hydroxyanisole, the 2, 6-di-tert-butyl-4-methylphenol and the hydroxyl acrylate monomer are completely dissolved, transferring the mixture into a constant-pressure dropping tank, slowly dropping the mixture into a reaction kettle at room temperature, continuing to react at room temperature for 30min after dropping, heating to 60-70 ℃ for reaction until the content of isocyanate groups (-NCO) of the mixture reaches a theoretical value (determined by a di-n-butylamine hydrochloride method), and cooling to obtain a prepolymer 2.
10. The preparation method of the hydrophilic wear-resistant photo-thermal dual-curing resin according to claim 1, wherein the prepolymer 2 is added into the hyperbranched resin in the step 4) and continuously reacted at 60-70 ℃ until the content of isocyanate group (-NCO) is zero to obtain the photo-thermal dual-curing resin, and the photo-thermal dual-curing resin is subjected to reduced pressure distillation to remove the solvent, drying, sealing and storing.
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