Triazine-containing photocurable resin and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9969703-B2
Application number	US-201615551594-A
Country	US
Kind code	B2
Filing date	Jan 20, 2016
Priority date	Jan 5, 2016
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

The present invention discloses a triazine-containing photocurable resin and a preparation method thereof. The preparation method of the resin comprises the following steps of: (1) Dissolving the hexamethylolmelamine the unsaturated fatty acids and a catalyst in a solvent, keeping a reaction going, separating and extracting the reaction product after the reaction ends, obtaining triazine-containing fatty acid ester; (2) adding 50 wt % hydrogen peroxide, a catalyst and a solvent, namely methylbenzene, into the triazine-containing fatty acid ester prepared in step (1), keeping a reaction going, obtaining triazine-containing fatty acid ester epoxy resin; (3) adding a polymerization inhibitor and a catalyst into acrylic acid, dropping the triazine-containing fatty acid ester epoxy resin prepared in step (2), keeping a reaction going, and obtaining the triazine-containing photocurable resin. The photocurable resin of the present invention contains a rigid triazine and flexible fatty chains at the same time, so the cured object has excellent comprehensive performance and can be used as the photocurable resin in the field of photosensitive macromolecular materials.

First claim

What is claimed is:

1. A preparation method of a triazine containing photocurable resin, comprising the following steps:
(1) dissolving a hexamethylolmelamine, an unsaturated fatty acid and a first catalyst in a first solvent to obtain a first solution, stirring the first solution at room temperature, heating the first solution refluxing for 20-48 h to form a plurality of first reaction products, separating and extracting the plurality of first reaction products to obtain a triazine-containing fatty acids ester;
(2) adding 50 wt % hydrogen peroxide, a second catalyst and a second solvent of methylbenzene into the triazine-containing fatty acids ester prepared in step (1) to obtain a second solution, stirring the second solution for 6-12 h at a temperature of 50-70° C. to obtain a second product, keeping the second reaction product still for layering, removing a water layer after layering, collecting an organic layer, washing the organic layer with a saturated aqueous solution of sodium bicarbonate and a de-ionized water until the organic layer is neutral, decompressing and distilling the neutral organic layer to remove the second solvent to obtain a triazine-containing fatty acid ester epoxy resin;
(3) adding a polymerization inhibitor and a third catalyst into an acrylic acid to obtain a mixed material, heating the mixed material to 85-105° C., dropping the triazine-containing fatty acid ester epoxy resin prepared in step (2) into the mixed material, keeping the mixed material at 80-105° C. for 4-8 h after the dropping is completed to obtain a triazine-containing photocurable resin.

2. The preparation method according to claim 1 , wherein in step (1), the unsaturated fatty acid is one or more selected from a group consisting of oleinic acid, linoleic acid, linolenic acid, arachidonic acid, petroselinic acid, eleostearic acid, calendula acid, erucic acid and palmitoleic acid; and a molar ratio of the hexamethylolmelamine to the unsaturated fatty acids is 1:6.0-12.0.

3. The preparation method according to claim 1 , wherein in step (1), the first catalyst is one or more selected from a group consisting of dicyclohexylcarbodiimide, 4-dimethylamino-pyridine, 1-(3 -dimethylaminopropyl)-3 -ethylcarbodiimide hydrochloride, sulfuric acid, benzenesulfonic acid, p-methylbenzene sulfonic acid and styrene sulfonic acid; and the first solvent is a solvent selected from a group consisting of dichloromethane, trichloromethane and methylbenzene.

4. The preparation method according to claim 1 , wherein in step (2), the second catalyst is one or more selected from a group consisting of formic acid, acetic acid and propanoic acid; and a molar ratio of the trizine ring-contained fatty acids ester to the hydrogen peroxide to the second catalyst is 1:1.4-2.2:0.4-0.7.

5. The preparation method according to claim 1 , wherein in step (3), the third catalyst is one or more selected from a group consisting of chromium 2-ethylhexanoate (III), triphenylphosphine, triethanolamine and tetrabutylammonium bromide, wherein an amount of the third catalyst accounts for 0.5-2.0% of a total mass of a reactants; the polymerization inhibitor is one or more selected from a group consisting of p-dihydroxybenzene, p-tert-butylhydroquinone and p-methoxyphenolate, wherein an amount of the polymerization inhibitor accounts for 0.10-0.30% of the total mass of the reactants; and a molar ratio of the acrylic acid to the triazine-containing fatty acid ester epoxy resin is 0.8-1.1:1.

6. The photocurable resin, wherein the photocurable resin comprising a triazin, wherein the structural formula of the photocurable resin is shown in formula (1):

wherein in the formula (1), the R group represents R 1 , R 2 , R 3 or R 4 ; wherein R 1 is:

R 2 is:

R 3 is:

and R 4 is:

wherein the 2 nd carbon atom of R 1 , R 2 , R 3 , and R 4 are linked to the —CO of formula (1).

7. The preparation method according to claim 1 , wherein in step (2), the method for preparing the triazine-containing fatty acid ester epoxy resin comprising steps of: adding a metachloroperbenzoic acid and a third solvent into the triazine-containing fatty acids ester prepared in step (1) to obtain a third solution, stirring the third solution for 3-24 h at a temperature of 0-30° C. to obtain a third reaction product, keeping the third reaction product still for layering, collecting the organic layer thereof, washing the organic layer using the saturated aqueous solution of sodium bicarbonate and de-ionized water in turn until the organic layer is neutral, decompressing and distilling the organic layer to remove the third solvent to obtain the triazine-containing fatty acid ester epoxy resin.

8. The preparation method according to claim 7 , wherein a molar ratio of the metachloroperbenzoic acid to the triazine-containing fatty acid ester is 0.8-2:1, and the third solvent is dichloromethane or trichloromethane.

Assignees

• Univ Jiangnan

Inventors

• Liu Ren
• Zhang Xiaopeng
• Li Zhiquan
• Liu Jingcheng
• Luo Jing
• Liu Xiaoya

Classifications

• C07D251/70 Primary

  Other substituted melamines · CPC title

• C08F220/283

  and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate · CPC title

• C08F22/22

  Esters containing nitrogen · CPC title

• C09D167/06

  Unsaturated polyesters having carbon-to-carbon unsaturation · CPC title