CN-121022262-B - Organic-inorganic hybridization modified aqueous bio-based photo-curing material and preparation method thereof

Abstract

The invention discloses an organic-inorganic hybridization modified water-based bio-based photo-curing material and a preparation method thereof, which adopts isocyanoethyl methacrylate to react with nano silicon dioxide to prepare modified nano silicon dioxide, then, the water-based bio-based photo-curing resin is successfully prepared by adopting citric acid, 3, 4-epoxy cyclohexyl methyl methacrylate, epoxy soybean oil and maleic anhydride, and finally, the water-based bio-based photo-curing material is prepared by compounding the modified nano silicon dioxide and the water-based bio-based photo-curing resin. The modified nano silicon dioxide is easy to be wetted and dispersed by the main resin, has good compatibility, can participate in the photo-curing reaction of the coating and form chemical crosslinking with the main resin, and has a synergistic effect with 3, 4-epoxy cyclohexyl methacrylate with a rigid six-membered ring structure, so that the cured material has the characteristics of high bio-base content, high mechanical property, high heat resistance, high pencil hardness and the like.

Inventors

• PENG JIE
• LIU YALI
• LI YOUJI
• YU XIHONG
• ZHANG XIAOPING
• TANG WEILIN

Assignees

• 吉首大学
• 湖南松井先进表面处理与功能涂层研究院有限公司

Dates

Publication Date

20260508

Application Date

20250820

Claims (8)

1. 1. The preparation method of the organic-inorganic hybridization modified water-based bio-based photo-curing material is characterized by comprising the following steps: step 1, dissolving and dispersing nano silicon dioxide in acetone to obtain nano silicon dioxide dispersion liquid; Step 2, mixing a polymerization inhibitor and nano silicon dioxide dispersion liquid in an inert atmosphere, adding a modified functional monomer with a monoisocyanate group and a double bond, heating to 50-70 ℃ for reaction for 2 hours, adding dibutyltin dilaurate, and continuously reacting for 12 hours at 50-70 ℃ to obtain modified nano silicon dioxide; Step 3, mixing citric acid, a polymerization inhibitor, a catalyst and 1, 4-dioxane under inert atmosphere, heating to 80-95 ℃, preserving heat until the citric acid is completely dissolved, dropwise adding methacrylic acid ester with an alicyclic structure, reacting for 0.5h, heating to 95-105 ℃ and continuing to react until the acid value is unchanged, adding epoxidized soybean oil, continuing to react for 1h at 95-110 ℃, controlling the temperature to 110 ℃, continuing to react until the acid value is unchanged, reducing the temperature of a reaction system to 80 ℃, and adding maleic anhydride, and reacting until the acid value is unchanged; Step 4, adding modified nano silicon dioxide, stirring until the mixture is fully and uniformly mixed, vacuumizing to remove the solvent, then reducing the temperature to 50-70 ℃, slowly adding triethylamine, adding deionized water under intense stirring and keeping for 0.5h, and filtering to obtain a product; and 5, adding a photoinitiator, a flatting agent and a defoaming agent into the product under the stirring state, and uniformly mixing to obtain the organic-inorganic hybrid modified aqueous bio-based photo-curing material.
2. 2. The preparation method according to claim 1, wherein in step 1-2, the mass percentages of the components are as follows:
3. 3. The method according to claim 2, wherein in step 1, the nanosilica is hydrophilic fumed silica; in the step 2, the modified functional monomer with a monoisocyanate group and a double bond is isocyanoethyl methacrylate; in the step 2, the polymerization inhibitor is one or a mixture of a plurality of hydroquinone, p-benzoquinone, p-tert-butylcatechol and p-methoxyphenol.
4. 4. The preparation method according to claim 1, wherein in the step 3-4, the mass percentages of the components are as follows:
5. 5. the method according to claim 4, wherein in the step 3, the polymerization inhibitors are one or a mixture of a plurality of hydroquinone, p-benzoquinone, p-tert-butylcatechol and p-methoxyphenol; In step 3, the methacrylate with an alicyclic structure is 3, 4-epoxycyclohexyl methacrylate; In the step 3, the catalyst is one of triphenylphosphine, N-dimethylaniline, N-dimethylbenzylamine and tetrabutylammonium bromide.
6. 6. The preparation method according to claim 1, wherein in step 5, the mass ratio of the photoinitiator is 2-5%, the mass ratio of the leveling agent is 0.05-0.5%, and the mass ratio of the defoaming agent is 0.1-1% based on the mass of the product prepared in step 4.
7. 7. The preparation method according to claim 6, wherein in the step 5, the photoinitiator is one or more of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether-phenyl acetone, 1-hydroxy-cyclohexyl benzophenone, and 2-hydroxy-2-methyl-1-phenyl acetone; The leveling agent is an organosilicon surface auxiliary agent; The defoaming agent is an organosilicon defoaming agent.
8. 8. An organic-inorganic hybrid modified aqueous bio-based photocurable material prepared by the preparation method according to any one of claims 1 to 7.

Description

Organic-inorganic hybridization modified aqueous bio-based photo-curing material and preparation method thereof Technical Field The invention relates to the technical field of water-based bio-based photo-curing materials, in particular to an organic-inorganic hybridization modified water-based bio-based photo-curing material and a preparation method thereof. Background The water-based bio-based photo-curing material is widely applied to various industries such as furniture, building, automobiles, electronics and packaging by virtue of the remarkable advantage of green environmental protection, and becomes a key material for reducing the emission of volatile organic compounds and improving the green sustainability in the coating industry. The soybean oil with rich yield is widely applied to the field of water-based bio-based photo-curing coatings. However, the soybean oil has poor mechanical properties, heat resistance, hardness and the like due to the existence of a large amount of long-chain aliphatic hydrocarbons in the molecular structure, and the application of the soybean oil in the fields of high performance and high added value is limited. Therefore, researchers develop intensive researches on how to improve the performance of the soybean oil-based water-based bio-based photo-curing coating, and explore various modification schemes so as to meet the higher requirements of different application scenes on the coating performance, and further expand the application field of the soybean oil-based water-based bio-based photo-curing coating. CN116217845A discloses a water-based bio-based photo-curing material and a preparation method thereof, the method adopts liquid bisphenol a epoxy resin and hydrogenated liquid bisphenol a epoxy resin as raw materials, and improves the mechanical property, heat resistance, adhesive force and other properties of the soybean oil-based water-based bio-based photo-curing coating. However, the proposal adopts petroleum-based epoxy resin for modification, which not only obviously reduces the content of biological base, but also has limited performance improvement effect. CN118006220a discloses a photo-thermal dual-curing-based aqueous bio-based photo-curing material and a preparation method thereof, and the method adopts a dual-curing process to improve the mechanical property, heat resistance, pencil hardness and other properties of the soybean oil-based aqueous bio-based photo-curing coating. However, the scheme adopts the water-based isocyanate curing agent added later, is a double-component material, is more complex than the single-component material in-situ preparation, is a double-curing process of photo-curing and then heat-curing, is complex in curing process, and is more energy-consuming than the pure photo-curing process, so that the green and energy-saving characteristics of the photo-curing process are lost. Disclosure of Invention In view of the defects existing at present, the invention provides an organic-inorganic hybridization modified water-based bio-based photo-curing material and a preparation method thereof, the invention adopts isocyanoethyl methacrylate to modify nano silicon dioxide, the modified nano silicon dioxide is easy to be wetted and dispersed by main resin and has good compatibility, and the nano silicon dioxide can also participate in photo-curing reaction of coating to form chemical crosslinking with the main resin; the modified nano silicon dioxide and the 3, 4-epoxy cyclohexyl methyl methacrylate with a rigid six-membered ring structure have synergistic effect, so that the cured material has the characteristics of high bio-base content, high mechanical property, high heat resistance and high pencil hardness, and has great application prospect in the fields of food packaging, medicine and health, children toys, automobile interiors, high-end printing and the like. In order to achieve the above object, the present invention provides a method for preparing an organic-inorganic hybrid modified aqueous bio-based photocurable material, comprising the steps of: step 1, dissolving and dispersing nano silicon dioxide in acetone to obtain nano silicon dioxide dispersion liquid; Step 2, mixing a polymerization inhibitor and nano silicon dioxide dispersion liquid in an inert atmosphere, adding a modified functional monomer with a monoisocyanate group and a double bond, heating to 50-70 ℃ for reaction for 2 hours, adding dibutyltin dilaurate, and continuously reacting for 12 hours at 50-70 ℃ to obtain modified nano silicon dioxide; Step 3, mixing citric acid, a polymerization inhibitor, a catalyst and 1, 4-dioxane under inert atmosphere, heating to 80-95 ℃, preserving heat until the citric acid is completely dissolved, dropwise adding methacrylic acid ester with an alicyclic structure, reacting for 0.5h, heating to 95-105 ℃ and continuing to react until the acid value is unchanged, adding epoxidized soybean oil, continuing to react for 1h at 95-110 ℃,