Search

CN-117466840-B - UV-curable modified epoxy vegetable oil acrylic ester, preparation method thereof and coating

CN117466840BCN 117466840 BCN117466840 BCN 117466840BCN-117466840-B

Abstract

The invention discloses a preparation method of UV-curable modified epoxy vegetable oil acrylic ester, which comprises the steps of mixing anhydride and polyol according to a molar ratio of 1:0.8-1.2, removing an organic solvent by rotary evaporation after reaction to obtain hydroxycarboxylic acid, mixing hydroxycarboxylic acid and methacrylic anhydride according to a molar ratio of 1:2-5, removing methacrylic acid by rotary evaporation after reaction to obtain a carboxyl-containing polyvinyl prepolymer, reacting the carboxyl-containing polyvinyl prepolymer with epoxidized vegetable oil in the presence of a catalyst and a polymerization inhibitor until the acid value is 2-20mgKOH/g, and cooling and discharging. The invention also discloses the UV-curable modified epoxy vegetable oil acrylic ester and the coating obtained by the preparation method. The UV-curable modified epoxy vegetable oil acrylic ester prepared by the invention has high vinyl functionality, high crosslinking density of cured coating film of the coating, and good alcohol resistance of the coating film, and can be used in the fields of woodware, furniture and plastic coating.

Inventors

  • QU JINQING
  • FENG LINXI
  • CHEN HUI

Assignees

  • 华南理工大学

Dates

Publication Date
20260505
Application Date
20230928

Claims (7)

  1. 1. The preparation method of the UV-curable modified epoxy vegetable oil acrylic ester is characterized by comprising the following steps of: (1) Preparing hydroxy carboxylic acid, namely mixing anhydride and polyalcohol according to a molar ratio of 1:0.8-1.2, adding an organic solvent to react for 2-3 hours at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain hydroxy carboxylic acid; The polyatomic alcohol is one of glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and trifunctional polyether N303, and the anhydride is one of phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, adipic anhydride, glutaric anhydride, itaconic anhydride and maleic anhydride; (2) The preparation of carboxyl-containing polyvinyl prepolymer comprises the steps of mixing hydroxycarboxylic acid and methacrylic anhydride according to a molar ratio of 1:2-5, adding a polymerization inhibitor, reacting for 2-4 hours at 80-100 ℃, and removing methacrylic acid by rotary evaporation to obtain carboxyl-containing polyvinyl prepolymer with vinyl functionality not less than 2; (3) The preparation of the UV-curable modified epoxy vegetable oil acrylic ester comprises the steps of mixing the carboxyl-containing polyvinyl prepolymer with the epoxidized vegetable oil according to the molar ratio of carboxyl to epoxy of 1:1.05-1.50, adding a catalyst accounting for 0.5-1.5% of the mass fraction of the epoxidized vegetable oil and a polymerization inhibitor accounting for 0.05-0.5% of the mass fraction of the carboxyl-containing polyvinyl prepolymer, reacting at 80-120 ℃ until the acid value is 2-20mgKOH/g, cooling, adding tripropylene glycol diacrylate, and discharging to obtain the UV-curable modified epoxy vegetable oil acrylic ester; The epoxidized vegetable oil is one of epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil and epoxidized dehydrated castor oil.
  2. 2. The method for preparing the UV curable modified epoxy vegetable oil acrylate according to claim 1, wherein the catalyst is one of N, N-dimethylbenzylamine, triphenylphosphine, tetraethylammonium bromide and tetrabutylammonium bromide.
  3. 3. The method for preparing the UV-curable modified epoxy vegetable oil acrylate according to claim 1, wherein the polymerization inhibitor is one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole and p-methoxyphenol.
  4. 4. The UV-curable modified epoxidized vegetable oil acrylate characterized by being prepared by the method for preparing the UV-curable modified epoxidized vegetable oil acrylate according to any one of claims 1 to 3.
  5. 5. A coating comprising the UV curable modified epoxidized vegetable oil acrylate of claim 4.
  6. 6. The coating according to claim 5, comprising, in parts by weight: 51.7-79.7 parts of UV curable modified vegetable oil acrylic ester, 10-45 parts of reactive diluent, 2-5 parts of photoinitiator and 0.2-0.6 part of auxiliary agent.
  7. 7. The coating of claim 6, wherein the reactive diluent is at least one of trimethylolpropane triacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, 1, 4-butanediol diacrylate; the photoinitiator is at least one of 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, 2-hydroxy-2 methyl-1 phenyl-1 acetone, 1-hydroxy-cyclohexyl phenyl ketone and isopropyl thioxanthone; The auxiliary agent comprises a leveling agent and a defoaming agent.

Description

UV-curable modified epoxy vegetable oil acrylic ester, preparation method thereof and coating Technical Field The invention relates to the field of preparation of ultraviolet light curing coatings, in particular to UV-curable modified epoxy vegetable oil acrylic ester, a preparation method thereof and a coating. Background The UV (ultraviolet) curing technology has been rapidly developed since the realization of industrialization in the last 60 th century, and has been widely used in the fields of paint, ink, 3D printing, and the like. At present, most of traditional photo-curing resins are derived from petrochemical resources, and along with exhaustion of global petroleum resources, renewable biomass such as vegetable oil is utilized to prepare high-performance UV-curable resins, so that the photo-curing resins have great significance for sustainable development of the coating industry. The epoxy vegetable oil is a universal green plasticizer, and is subjected to acrylic acid, so that the UV curable epoxy vegetable oil acrylic ester is obtained. Epoxy soybean oil acrylate (AESO for short) is commercialized, the functionality of vinyl (C=C-) is not high, the crosslinking density of a cured coating film is low, and the chemical resistance of the coating is not good. The patent application with publication number CN 102660170A discloses the application of acrylic ester modified epoxidized soybean oil in preparing paper printing ink, which is to react an acrylic ester monomer containing hydroxyl with anhydride to obtain a half-ester intermediate, and then react with epoxidized soybean oil to obtain epoxidized soybean oil modified acrylic ester. The patent application with publication number CN 102660387A discloses an acrylic ester modified epoxy soybean oil, a preparation method and application thereof, which is obtained by reacting hydroxyl-containing acrylic ester monomer with anhydride to obtain half-ester intermediate and then reacting with epoxy soybean oil, wherein the hydroxyl-containing acrylic ester monomer is hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate or trimethylolpropane dimethacrylate, the hydroxyl-containing acrylic acid monomer, especially the multi-vinyl functional monomer, is expensive, and the modified product still has the defects of low vinyl functionality, low coating crosslinking density, insufficient chemical resistance and the like. Disclosure of Invention In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of UV-curable modified epoxy vegetable oil acrylic ester, wherein the prepared epoxy vegetable oil acrylic acid has higher vinyl functionality and better coating hardness and chemical resistance, and meanwhile, the adopted raw materials are epoxy vegetable oil, polyalcohol, anhydride and the like, so that the source is wide, the price is low, the product cost is low, and hydroxyl acrylic monomers such as pentaerythritol triacrylate and trimethylolpropane diacrylate with high cost are not used. The invention also aims to provide the UV-curable modified epoxy vegetable oil acrylic ester prepared by the preparation method. It is still another object of the present invention to provide a coating material which has a high crosslinking density and a good chemical resistance of a cured coating film. The aim of the invention is achieved by the following technical scheme: the preparation method of the UV-curable modified epoxy vegetable oil acrylic ester comprises the following steps: (1) Preparing hydroxy carboxylic acid, namely mixing anhydride and polyalcohol according to a molar ratio of 1:0.8-1.2, adding an organic solvent to react for 2-3 hours at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain hydroxy carboxylic acid; the polyol is a polyol having a hydroxyl functionality of not less than 3; (2) The preparation of carboxyl-containing polyvinyl prepolymer comprises the steps of mixing hydroxycarboxylic acid and methacrylic anhydride according to a molar ratio of 1:2-5, adding a polymerization inhibitor, reacting for 2-4 hours at 80-100 ℃, and removing methacrylic acid by rotary evaporation to obtain carboxyl-containing polyvinyl prepolymer with vinyl functionality not less than 2; (3) The preparation of the UV-curable modified epoxy vegetable oil acrylic ester comprises the steps of mixing the carboxyl-containing polyvinyl prepolymer with the epoxidized vegetable oil according to the molar ratio of carboxyl to epoxy of 1:1.05-1.50, adding a catalyst accounting for 0.5-1.5% of the mass fraction of the epoxidized vegetable oil and a polymerization inhibitor accounting for 0.05-0.5% of the mass fraction of the carboxyl-containing polyvinyl prepolymer, reacting at 80-120 ℃ until the acid value is 2-20mgKOH/g, cooling, adding tripropylene glycol diacrylate, and discharging to obtain