CN108409953B - Tri-functionality epoxy acrylic resin and preparation method and application thereof - Google Patents
Tri-functionality epoxy acrylic resin and preparation method and application thereof Download PDFInfo
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- CN108409953B CN108409953B CN201810271944.0A CN201810271944A CN108409953B CN 108409953 B CN108409953 B CN 108409953B CN 201810271944 A CN201810271944 A CN 201810271944A CN 108409953 B CN108409953 B CN 108409953B
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- C08G63/91—Polymers modified by chemical after-treatment
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Abstract
The invention discloses a trifunctional epoxy acrylic resin, a preparation method and application thereof, and the resin has the following structural formula:
Description
Technical Field
The invention belongs to the technical field of photocuring materials, and particularly relates to a trifunctional epoxy acrylic resin, and a preparation method and application thereof.
Background
The photocuring material is a new material with high efficiency, energy conservation, economy, environmental protection and wide adaptability, and particularly, because the country limits the use of solvents, the photocuring material is increasingly regarded as an environment-friendly material. Among them, epoxy acrylate resin is the most widely used light-cured oligomer with the largest market demand at present, and is more and more widely used in the industries of coatings, printing inks, adhesives and the like, and has replaced the traditional solvent-containing material in many fields.
Currently, the epoxy acrylic resins on the market are basically of several types: bisphenol a epoxy acrylates, novolac epoxy acrylates, various modified epoxy acrylates and epoxidized oil acrylates. The bisphenol A epoxy acrylate is used in the largest amount, but the light aging resistance and the yellowing resistance are poor. The various modified epoxy acrylates are essentially bisphenol a type and also suffer from poor resistance to photoaging and yellowing. The phenolic epoxy acrylate is multifunctional resin, but the viscosity of the phenolic epoxy acrylate is higher, and the curing speed of the epoxy oil acrylate is too slow, so that the phenolic epoxy acrylate can only be matched with other resin with high activity for use.
Disclosure of Invention
In order to solve the above-mentioned problems of the prior art, the primary object of the present invention is to provide a trifunctional epoxy acrylic resin, which has the advantages of low viscosity, fast curing speed, good resistance to light aging and yellowing.
Another object of the present invention is to provide a method for preparing the above trifunctional epoxy acrylic resin.
The invention is realized by the following technical scheme:
a trifunctional epoxy acrylic resin having the formula:
R3represents H or CH3；
n=0～5000。
The trifunctional epoxy acrylic resin is prepared from the following components in parts by weight:
(A) 15-50 parts of trifunctional polyol
(B) 25-65 parts of acid anhydride
(C) 25-60 parts of alicyclic epoxy acrylate
(D) 10.02-0.5 parts of catalyst
(E) 20.02-0.5 parts of catalyst
(F) 0.02-0.5 part of polymerization inhibitor.
The trifunctional polyalcohol is one or more of trimethylolpropane, trimethylolethane, glycerol, hexanetriol, trihydroxyethyl isocyanurate, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, caprolactonized trimethylolpropane, ethoxylated trimethylolethane, propoxylated trimethylolethane, caprolactonized trimethylolethane, ethoxylated glycerol, propoxylated glycerol, caprolactonized glycerol, ethoxylated hexanetriol, propoxylated hexanetriol, ethoxylated trihydroxyethyl isocyanurate, propoxylated trihydroxyethyl isocyanurate or caprolactonized trihydroxyethyl isocyanurate.
The anhydride is one or a mixture of more of succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride or cyclopentene dicarboxylic anhydride.
The alicyclic epoxy acrylate is one or a mixture of 3, 4-epoxy cyclohexyl methyl acrylate or 3, 4-epoxy cyclohexyl methyl acrylate.
The catalyst 1 is one or a mixture of several of organic tin catalysts or organic bismuth catalysts.
The catalyst 2 is one or a mixture of triphenylphosphine, tetrabutylammonium bromide or triethylbenzylammonium chloride.
The polymerization inhibitor is one or a mixture of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
The viscosity of the three-functionality epoxy acrylic resin at 25 ℃ is 30000-.
The invention also provides a preparation method of the epoxy acrylic resin with three functionality degrees, which comprises the following steps:
adding 13-43 parts by weight of polyol, 22-62 parts by weight of anhydride and 0.02-0.5 part by weight of catalyst 1 into a reaction container, heating to 70-130 ℃, stirring for reaction for 3-6 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 26-63 parts by weight of alicyclic epoxy acrylate, 0.02-0.5 part by weight of polymerization inhibitor and 0.02-0.5 part by weight of catalyst 2 into the reaction container, heating to 80-140 ℃, and cooling to discharge transparent colorless or light yellow liquid resin which is trifunctional epoxy acrylic resin when the acid value is measured to be less than 5 mgKOH/g.
The invention also provides the application of the trifunctional epoxy acrylic resin in paint, ink or adhesive.
Compared with the prior art, the invention has the following beneficial effects:
(1) the alicyclic epoxy acrylate is introduced to replace the traditional bisphenol A epoxy acrylate and phenolic epoxy acrylate, so that the viscosity of the prepared trifunctional epoxy acrylate resin is greatly reduced, the production process is greatly simplified, and meanwhile, the problems of poor light aging resistance and yellowing resistance of the traditional epoxy acrylate resin are solved;
(2) by introducing the trifunctional polyalcohol, the novel structure is different from the structure that the traditional epoxy acrylate resin is mostly bifunctional, so that the curing speed and the hardness of the epoxy acrylate resin are greatly improved, and the application of the epoxy acrylate resin is further widened.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the embodiments of the present invention, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions and alterations are intended to be included in the scope of the present invention.
Example 1:
adding 18 parts by weight of trimethylolpropane, 40 parts by weight of maleic anhydride and 0.1 part by weight of organic tin catalyst into a reaction vessel, heating to 100 ℃, stirring for reaction for 5 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 80 parts by weight of 3, 4-epoxy cyclohexyl methyl methacrylate, 0.1 part by weight of hydroquinone and 0.1 part by weight of tetrabutylammonium bromide into the reaction vessel, heating to 110 ℃, and cooling and discharging transparent colorless or light yellow liquid resin which is trifunctional epoxy acrylic resin A when the acid value is measured to be less than 5 mgKOH/g.
The viscosity, curing speed and weather resistance of the trifunctional epoxy acrylic resin prepared by the method are shown in Table 1.
Example 2:
adding 25 parts by weight of hexanetriol, 50 parts by weight of succinic anhydride and 0.2 part by weight of organic bismuth catalyst into a reaction vessel, heating to 90 ℃, stirring for reacting for 6 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 50 parts by weight of 3, 4-epoxy cyclohexyl methacrylate, 0.2 part by weight of hydroquinone and 0.2 part by weight of triphenylphosphine into the reaction vessel, heating to 120 ℃, and cooling and discharging until the acid value is measured to be less than 5mgKOH/g, wherein the transparent colorless or light yellow liquid resin is the trifunctional epoxy acrylic resin B.
The viscosity, curing speed and weather resistance of the trifunctional epoxy acrylic resin prepared by the method are shown in Table 1.
Example 3:
adding 20 parts by weight of ethoxylated trishydroxyethyl isocyanurate, 30 parts by weight of glutaric anhydride and 0.1 part by weight of organic tin catalyst into a reaction vessel, heating to 110 ℃, stirring for reaction for 4 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 30 parts by weight of 3, 4-epoxycyclohexyl methacrylate, 0.1 part by weight of hydroquinone and 0.1 part by weight of tetrabutylammonium bromide into the reaction vessel, heating to 100 ℃, and cooling and discharging transparent colorless or light yellow liquid resin which is epoxy acrylic resin C with three functionality degrees until the acid value is measured to be less than 5 mgKOH/g.
The viscosity, curing speed and weather resistance of the trifunctional epoxy acrylic resin prepared by the method are shown in Table 1.
Example 4:
adding 30 parts by weight of glycerol, 45 parts by weight of cyclopentene dicarboxylic anhydride and 0.1 part by weight of organic tin catalyst into a reaction vessel, heating to 120 ℃, stirring for reaction for 3 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 45 parts by weight of 3, 4-epoxy cyclohexyl methacrylate, 0.1 part by weight of hydroquinone and 0.1 part by weight of tetrabutylammonium bromide into the reaction vessel, heating to 95 ℃, and cooling and discharging to obtain transparent colorless or light yellow liquid resin which is trifunctional epoxy acrylic resin D when the acid value is measured to be less than 5 mgKOH/g.
The viscosity, curing speed and weather resistance of the trifunctional epoxy acrylic resin prepared by the method are shown in Table 1.
Example 5:
adding 40 parts by weight of ethoxylated trimethylolpropane, 25 parts by weight of succinic anhydride and 0.1 part by weight of organic tin catalyst into a reaction vessel, heating to 95 ℃, stirring for reaction for 5 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 35 parts by weight of 3, 4-epoxycyclohexyl methacrylate, 0.1 part by weight of hydroquinone and 0.1 part by weight of tetrabutylammonium bromide into the reaction vessel, heating to 115 ℃, and cooling and discharging until the acid value is measured to be less than 5mgKOH/g, wherein the transparent colorless or light yellow liquid resin is trifunctional epoxy acrylic resin E.
The viscosity, curing speed and weather resistance of the trifunctional epoxy acrylic resin prepared by the method are shown in Table 1.
Comparative example 1:
adding 18 parts by weight of trimethylolpropane, 40 parts by weight of maleic anhydride and 0.1 part by weight of organic tin catalyst into a reaction vessel, heating to 100 ℃, stirring for reaction for 5 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 150 parts by weight of bisphenol A epoxy resin, 0.1 part by weight of hydroquinone, 0.1 part by weight of tetrabutylammonium bromide and 29 parts by weight of acrylic acid into the reaction vessel, heating to 110 ℃, and cooling and discharging transparent colorless or light yellow liquid resin which is trifunctional epoxy acrylic resin F when the acid value is measured to be less than 5 mgKOH/g.
The viscosity, curing speed and weather resistance of the trifunctional epoxy acrylic resin prepared by the method are shown in Table 1.
Comparative example 2:
adding 40 parts by weight of novolac epoxy resin, 0.1 part by weight of hydroquinone, 0.1 part by weight of tetrabutylammonium bromide and 15 parts by weight of acrylic acid into a reaction vessel, heating to 110 ℃, and cooling and discharging when the measured acid value is less than 5mgKOH/G, wherein the obtained product is epoxy acrylic resin G which is transparent colorless or light yellow liquid resin.
The viscosity, curing speed and weather resistance of the epoxy acrylic resin prepared by the method are shown in Table 1.
TABLE 1 results of performance test of examples and comparative examples
| Viscosity cps/25 deg.C | Curing energy mJ/cm2 | Weather resistance | ||
| Example 1 | Resin A | 34572 | 73 | Ok |
| Example 2 | Resin B | 33498 | 75 | Ok |
| Example 3 | Resin C | 40235 | 73 | Ok |
| Example 4 | Resin D | 36723 | 73 | Ok |
| Example 5 | Resin E | 38375 | 76 | Ok |
| Comparative example 1 | Resin F | 142293 | 85 | Yellowing of |
| Comparative example 2 | Resin G | 201232 | 81 | Slightly yellow |
Each performance test method or standard:
viscosity: GB/T10247-2008
Weather resistance: GB 1767-7989.
Claims (8)
1. A trifunctional epoxy acrylic resin having the formula:
the viscosity of the three-functionality epoxy acrylic resin at 25 ℃ is 30000-.
2. The trifunctional epoxy acrylic resin of claim 1, wherein the trifunctional epoxy acrylic resin is prepared from the following components in parts by weight:
(A) 13-43 parts of trifunctional polyol
(B) 22-62 parts of acid anhydride
(C) 26-63 parts of alicyclic epoxy acrylate
(D) 10.02-0.5 parts of catalyst
(E) 20.02-0.5 parts of catalyst
(F) 0.02-0.5 part of polymerization inhibitor.
3. The trifunctional epoxy acrylic resin of claim 2, wherein the trifunctional polyol is one or a mixture of trimethylolpropane, trimethylolethane, glycerol, hexanetriol, trishydroxyethyl isocyanurate, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, caprolactozed trimethylolpropane, ethoxylated trimethylolethane, propoxylated trimethylolethane, caprolactozed trimethylolethane, ethoxylated glycerol, propoxylated glycerol, caprolactozed glycerol, ethoxylated hexanetriol, propoxylated hexanetriol, ethoxylated trishydroxyethyl isocyanurate, propoxylated trishydroxyethyl isocyanurate or caprolactozed trishydroxyethyl isocyanurate.
4. The trifunctional epoxy acrylic resin of claim 2, wherein the anhydride is one or more of succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and cyclopentene dicarboxylic anhydride.
5. The trifunctional epoxy acrylate resin of claim 2, wherein the alicyclic epoxy acrylate is one or a mixture of 3, 4-epoxycyclohexyl methacrylate and 3, 4-epoxycyclohexyl methacrylate.
6. The trifunctional epoxy acrylic resin of claim 2, wherein the catalyst 1 is one or a mixture of organic tin catalyst and organic bismuth catalyst; the catalyst 2 is one or a mixture of more of triphenylphosphine, tetrabutylammonium bromide or triethylbenzylammonium chloride; the polymerization inhibitor is one or a mixture of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
7. A process for preparing a trifunctional epoxy acrylic resin as claimed in any one of claims 1 to 6, comprising the steps of:
adding 13-43 parts by weight of trifunctional polyol, 22-62 parts by weight of anhydride and 0.02-0.5 part by weight of catalyst 1 into a reaction container, heating to 70-130 ℃, stirring for reaction for 3-6 hours, cooling to room temperature when the acid value is measured to 1/2 +/-3% of the total acid value before heating, adding 26-63 parts by weight of alicyclic epoxy acrylate, 0.02-0.5 part by weight of polymerization inhibitor and 0.02-0.5 part by weight of catalyst 2 into the reaction container, heating to 80-140 ℃, and cooling to discharge transparent colorless or light yellow liquid resin which is trifunctional epoxy acrylate resin when the acid value is measured to be less than 5 mgKOH/g.
8. Use of a trifunctional epoxy acrylic resin according to any of claims 1 to 6 in coatings, inks or adhesives.
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| CN111394001B (en) * | 2020-04-28 | 2021-09-17 | 广东硕成科技有限公司 | High-pressure forming protective film for mobile phone back cover and preparation method thereof |
| CN112552854A (en) * | 2020-12-18 | 2021-03-26 | 山东万圣博化工有限公司 | Conductive adhesive and preparation method thereof |
| CN113912823A (en) * | 2021-09-23 | 2022-01-11 | 肇庆市宝骏化工有限公司 | Polyurethane and anhydride modified hydrogenated bisphenol A epoxy acrylic resin and preparation method and application thereof |
| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
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