WO2022133679A1 - 一种uv固化亮光树脂及其制备方法 - Google Patents

一种uv固化亮光树脂及其制备方法 Download PDF

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WO2022133679A1
WO2022133679A1 PCT/CN2020/138097 CN2020138097W WO2022133679A1 WO 2022133679 A1 WO2022133679 A1 WO 2022133679A1 CN 2020138097 W CN2020138097 W CN 2020138097W WO 2022133679 A1 WO2022133679 A1 WO 2022133679A1
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resin
curable
bright
extract
parts
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PCT/CN2020/138097
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English (en)
French (fr)
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张佩嫦
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张佩嫦
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Definitions

  • the invention relates to the technical field of paint production, in particular to a UV-curable bright resin and a preparation method thereof.
  • UV curing is a process in which the photoinitiator in the liquid UV material is converted into free radicals or cations under the irradiation of medium and short wavelengths of UV, thereby triggering the polymerization and crosslinking of the resin containing active functional groups into an insoluble and infusible solid coating film.
  • white-based paints require resins with bright white properties, including high hardness, high gloss, yellowing resistance, and bright white transparency.
  • the present invention provides a UV-curable bright resin containing unsaturated double bonds with better comprehensive properties and a preparation method thereof.
  • the present invention makes the resin have high double bond density by introducing a large number of multifunctional hydroxy acrylates, and has high hardness and high gloss after curing; and by using a specific epoxy resin 1-4 butanediol diglycidyl ether, it is Excellent yellowing resistance is brought into the molecule, and the synthesized resin has excellent whitening properties.
  • the present invention provides the following technical solutions:
  • a UV-curable bright resin in parts by weight, comprising the following components:
  • a UV-curable bright resin in parts by weight, comprising the following components:
  • the hydroxy acrylic resin is one or more of pentaerythritol triacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. any combination of species.
  • the acid anhydride is at least one of hexahydrophthalic anhydride or succinic anhydride.
  • the polymerization inhibitor is at least one of p-hydroxyanisole or hydroquinone.
  • the catalyst is at least one of triphenylphosphine, triethylamine or benzyltriethylammonium chloride.
  • the antioxidant is one or any combination of hypophosphorous acid, 2,6-di-tert-butylphenol, and phenol.
  • the epoxy resin is 1,4-butanediol diglycidyl ether.
  • the guava seed extract is a polyphenolic substance; the guava seed extract is mainly a guava seed polyphenol extract, which has an antioxidant effect and can enhance the weather resistance of the resin , to prevent its yellowing.
  • the grape seed extract is a class of polyphenols extracted and separated from grape seeds, which mainly include polyphenols such as proanthocyanidins, catechins, epicatechins, gallic acid, and epicatechin gallate. substance. These polyphenols have anti-oxidation ability, mainly due to their rich double bonds, which can be compounded with resins to make the resins have high double bond density, high hardness and high gloss after curing.
  • the eucalyptus leaf ethanolic extract is prepared by the following method:
  • the ethanolic extract of eucalyptus leaves is rich in eucalyptus oil, which mainly contains pinene, 1,8-cineole, phellandrene, citronene, allohemanerene, caryophyllene and rosinol, etc., which have antibacterial and Deodorant effect. It contains olefinic compounds and also has abundant double bonds, which increases the density of double bonds.
  • the present invention also provides a method for preparing the above-mentioned UV-curable bright resin, which is prepared according to the following steps:
  • Step 1) in parts by weight, sequentially drop hydroxy acrylate, acid anhydride, antioxidant and polymerization inhibitor into the reactor, heat up to 40 ⁇ 50 °C, and stir until dissolved;
  • Step 3) cool down to 90°C, put in epoxy resin, catalyst and unsaturated polyester, slowly heat up to 95°C and keep for 1h;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add guava seed extract, grape seed extract and eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge;
  • the above synthesis process controls the degree of reaction by titrating acid value and viscosity.
  • the UV-curable bright resin provided by the present invention is by introducing polyfunctional hydroxy acrylate into the structure, and the high double bond density makes the surface after light curing very tight, with high hardness and high gloss. and other properties;
  • the epoxy resin used is a specific 1,4-butanediol diglycidyl ether, which is a simple aliphatic epoxy resin and does not contain benzene rings and other structures that are prone to yellowing.
  • the modified epoxy resin obtained by the reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 39g hydroxyethyl acrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyl Phenyl ether, 182 g of 1,4-butanediol diglycidyl ether, 4 g of triphenylphosphine and 46 g of self-produced unsaturated polyester.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) drop into the reaction kettle successively 525g pentaerythritol triacrylate, 39g hydroxyethyl acrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether, be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) Cool to 90°C, put in 182g 1,4-butanediol diglycidyl ether, 4g triphenylphosphine, 46g self-produced unsaturated polyester, slowly heat up to 95°C and keep for 1h;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.1g guava seed extract, 0.15g grape seed extract and 0.2g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 43.7g hydroxypropyl acrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g paraffin Hydroxyphenyl ether, 182 g of 1,4-butanediol diglycidyl ether, 4 g of triphenylphosphine and 46 g of self-produced unsaturated polyester.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) successively drop into 525g pentaerythritol triacrylate, 43.7g hydroxypropyl acrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether in the reaction kettle, be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) cool down to 90°C, put in 182g of 1,4-butanediol diglycidyl ether, 4g of triphenylphosphine, 46g of self-produced unsaturated polyester, slowly heat up to 95°C for 1 hour;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.3g guava seed extract, 0.2g grape seed extract and 0.3g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 43.7g hydroxyethyl methacrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g g p-hydroxyphenyl ether, 182 g 1,4-butanediol diglycidyl ether, 4 g triphenylphosphine and 46 g self-produced unsaturated polyester.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) put 525g pentaerythritol triacrylate, 43.7g hydroxyethyl methacrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether successively in the reactor, Heat up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) cool down to 90°C, put in 182g of 1,4-butanediol diglycidyl ether, 4g of triphenylphosphine, 46g of self-produced unsaturated polyester, slowly heat up to 95°C for 1 hour;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.15g guava seed extract, 0.25g grape seed extract and 0.35g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 48.4g hydroxypropyl methacrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g g p-hydroxyphenyl ether.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) 525g pentaerythritol triacrylate, 48.4g hydroxypropyl methacrylate, 200g hexahydrophthalic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether, 182g 1,4-butanediol diglycidyl ether, 4g triphenylphosphine and 46g self-produced unsaturated polyester, heat up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) cool down to 90°C, put in 182g of 1,4-butanediol diglycidyl ether, 4g of triphenylphosphine, 46g of self-produced unsaturated polyester, slowly heat up to 95°C for 1 hour;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.1g guava seed extract, 0.125g grape seed extract and 0.3g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 39g hydroxyethyl acrylate, 130g succinic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyl Phenyl ether, 182 g of 1,4-butanediol diglycidyl ether, 4 g of triphenylphosphine and 46 g of self-produced unsaturated polyester.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) drop into the reaction kettle successively 525g pentaerythritol triacrylate, 39g hydroxyethyl acrylate, 130g succinic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether, be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) cool down to 90°C, put in 182g of 1,4-butanediol diglycidyl ether, 4g of triphenylphosphine, 46g of self-produced unsaturated polyester, slowly heat up to 95°C for 1 hour;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.1g guava seed extract, 0.1g grape seed extract and 0.5g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 43.7g hydroxypropyl acrylate, 130g succinic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyl Phenyl ether, 182 g of 1,4-butanediol diglycidyl ether, 4 g of triphenylphosphine and 46 g of self-produced unsaturated polyester.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) successively drop in 525g pentaerythritol triacrylate, 43.7g hydroxypropyl acrylate, 130g succinic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether in the reaction kettle, be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) cool down to 90°C, put in 182g of 1,4-butanediol diglycidyl ether, 4g of triphenylphosphine, 46g of self-produced unsaturated polyester, slowly heat up to 95°C for 1 hour;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.2g guava seed extract, 0.2g grape seed extract and 0.2g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.
  • a UV-curable bright resin in parts by weight, comprising the following components: 525g pentaerythritol triacrylate, 43.7g hydroxypropyl methacrylate, 130g succinic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether, 182 g of 1,4-butanediol diglycidyl ether, 4 g of triphenylphosphine and 46 g of self-produced unsaturated polyester.
  • the preparation method of this UV curing bright resin is prepared according to the following steps:
  • Step 1) put 525g pentaerythritol triacrylate, 43.7g hydroxypropyl methacrylate, 130g succinic anhydride, 0.5g 2,6-di-tert-butylphenol, 0.6g p-hydroxyphenyl ether successively in the reactor, Heat up to 40 ⁇ 50°C, stir until dissolved;
  • Step 3) cool down to 90°C, put in 182g of 1,4-butanediol diglycidyl ether, 4g of triphenylphosphine, 46g of self-produced unsaturated polyester, slowly heat up to 95°C for 1 hour;
  • Step 5 measure the acid value, when Av ⁇ 4mgKOH/g, add 0.3g guava seed extract, 0.1g grape seed extract and 0.5g eucalyptus leaf ethanol extract when cooling to normal temperature, and discharge.
  • the UV-curable bright resin does not contain benzene rings and other structures prone to yellowing, the modified epoxy resin obtained by simple reaction has excellent resistance to yellowing, and the paint film is bright white and transparent.

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Abstract

一种UV固化亮光树脂，按重量份数，包括以下组分：羟基丙烯酸酯50～60份，酸酐20～30份，抗氧剂0～0.2份，阻聚剂0～0.1份，环氧树脂15～30份，催化剂0～0.8份，不饱和聚酯3～8份，番石榴籽提取物0.02～0.15份，葡萄籽提取物0.1～0.15份，桉树叶乙醇提取物0.1～0.5份。通过引入大量多官能团的羟基丙烯酸酯使得树脂具有高的双键密度，固化后具有高硬度、高光泽；并通过使用特定的环氧树脂1-4丁二醇二缩水甘油醚，将其优异的耐黄变性能带入分子中，合成的树脂具有优异的亮白性能。

Description

一种UV固化亮光树脂及其制备方法 技术领域
本发明涉及涂料生产的技术领域，尤其是涉及一种UV固化亮光树脂及其制备方法。
背景技术
UV固化是在UV的中、短波辐照下，液态UV材料中的光引发剂转变为自由基或阳离子，从而引发含活性官能团的树脂聚合交联成不溶不熔的固体涂膜的过程。因具有高效、经济、节能、适用性广和环境友好的优点，UV固化技术广泛应用于涂料、油墨、胶粘剂等领域。
但现有的紫外光固化树脂由于在成膜后，由于环境的关系，树脂一般会发生黄变，影响外观。
在涂料等领域中，白底的油漆需要树脂具有亮光白的性能，既需要有高硬度、高光泽、耐黄变并且亮白透明。
因此，如何提供一种可UV固化亮光树脂，是本领域的技术人员需要解决的技术问题。
发明内容
为了解决现有技术存在的上述问题，本发明提供了综合性能较好的含有不饱和双键的UV固化亮光树脂及其制备方法。本发明通过引入大量多官的羟基丙烯酸酯使得树脂具有高的双键密度，固化后具有高硬度、高光泽；并通过使用特定的环氧树脂1-4丁二醇二缩水甘油醚，将其优异的耐黄变性能带入分子中，合成的树脂具有优异的亮白性能。
为了实现上述目的，本发明提供了如下技术方案：
一种UV固化亮光树脂，按重量份数，包括以下组分：
Figure PCTCN2020138097-appb-000001
Figure PCTCN2020138097-appb-000002
一种UV固化亮光树脂，按重量份数，包括以下组分：
Figure PCTCN2020138097-appb-000003
作为本发明的技术方案的进一步描述，所述羟基丙烯酸树脂为季戊四醇三丙烯酸酯与丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯，甲基丙烯酸羟丙酯中的一种或者几种的任意组合。
作为本发明的技术方案的进一步描述，所述酸酐为六氢苯酐或丁二酸酐中的至少一种。
作为本发明的技术方案的进一步描述，所述阻聚剂为对羟基苯甲醚或对苯二酚的至少一种。
作为本发明的技术方案的进一步描述，所述催化剂为三苯基膦、三乙胺或苄基三乙基氯化铵中的至少一种。
作为本发明的技术方案的进一步描述，所述抗氧剂为次磷酸、2,6-二叔丁基苯酚、苯酚中的一种或者几种的任意组合。
作为本发明的技术方案的进一步描述，所述环氧树脂为1,4-丁二醇二缩水甘油醚。
作为本发明的技术方案的进一步描述，所述番石榴籽提取物为多酚类物质；番石 榴籽提取物主要为番石榴籽多酚提取物，其具有抗氧化作用，可增强树脂的耐候性，防止其黄变。
所述葡萄籽提取物是从葡萄籽中提取分离得到的一类多酚类物质，其主要包括原花青素、儿茶素、表儿茶素、没食子酸、表儿茶素没食子酸酯等多酚类物质。这些多酚类物质有抗氧化能力，主要原因在于其有丰富的双键，其与树脂复配，可以使得树脂具有高的双键密度，固化后具有高硬度、高光泽。
所述桉树叶乙醇提取物按以下方法制备得到：
(1)向盛有桉树叶的容器中加入70-80％乙醇，回流提取3次，每次1h，经100目筛过滤后，合并滤液，得桉树叶醇提取液；
(2)加入活性炭进行脱色，将脱色后的桉树叶醇提取液经喷雾干燥，得到桉树叶乙醇提取物。
桉树叶乙醇提取物富含桉叶油，油中主含蒎烯、1,8-桉叶素、水芹烯、香橙烯、别香橙烯、石竹烯和松香芹醇等，有抗菌和除臭的作用。其含有烯类化合物，也有丰富的双键，提高双键密度。
本发明还提供了上述UV固化亮光树脂的制备方法，按以下步骤进行制备：
步骤1)：按重量份数，在反应釜中依次投入羟基丙烯酸酯、酸酐、抗氧剂和阻聚剂，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入环氧树脂、催化剂和不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入番石榴籽提取物、葡萄籽提取物和桉树叶乙醇提取物，出料；
上述合成过程通过滴定酸值和粘度控制反应程度。
基于上述的技术方案，本发明取得的技术效果为：
相对于现有技术，本发明所提供的可紫外光固化亮光树脂是通过将多官的羟基丙烯酸酯引入结构中，高的双键密度使得光固化后的表面十分紧密，具有高硬度、高光泽等性能；使用的环氧树脂为特定的1,4-丁二醇二缩水甘油醚，该环氧树脂为简单的脂肪族环氧树脂，不含苯环等易黄变的结构，通过简单的反应得到 的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
具体实施方式
为了便于理解本发明，下面将结合具体的实施例对本发明进行更全面的描述。本发明给出了的较佳实施方式。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明。
实施例1
一种UV固化亮光树脂，按重量份数，包括以下组分：525g季戊四醇三丙烯酸酯、39g丙烯酸羟乙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g 1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不饱和聚酯。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、39g丙烯酸羟乙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g 1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.1g番石榴籽提取物、0.15g葡萄籽提取物和0.2g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
实施例2
一种UV固化亮光树脂，按重量份数，包括以下组分：525g季戊四醇三丙烯酸酯、43.7g丙烯酸羟丙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不 饱和聚酯。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、43.7g丙烯酸羟丙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.3g番石榴籽提取物、0.2g葡萄籽提取物和0.3g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
实施例3
一种UV固化亮光树脂，按重量份数，包括以下组分：525g季戊四醇三丙烯酸酯、43.7g甲基丙烯酸羟乙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g 1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不饱和聚酯。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、43.7g甲基丙烯酸羟乙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.15g番石榴籽提取物、0.25g葡萄籽提取物和0.35g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
实施例4
一种UV固化亮光树脂，按重量份数，包括以下组分：525g季戊四醇三丙烯酸酯、48.4g甲基丙烯酸羟丙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、48.4g甲基丙烯酸羟丙酯、200g六氢苯酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g 1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不饱和聚酯，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.1g番石榴籽提取物、0.125g葡萄籽提取物和0.3g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
实施例5
一种UV固化亮光树脂，按重量份数，包括以下组分：525g季戊四醇三丙烯酸酯、39g丙烯酸羟乙酯、130g丁二酸酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不饱和聚酯。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、39g丙烯酸羟乙酯、130g丁二酸酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.1g番石榴籽提取物、0.1g葡萄籽提取物和0.5g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
实施例6
一种UV固化亮光树脂，按重量份数，包括以下组分525g季戊四醇三丙烯酸酯、43.7g丙烯酸羟丙酯、130g丁二酸酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不饱和聚酯。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、43.7g丙烯酸羟丙酯、130g丁二酸酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.2g番石榴籽提取物、0.2g葡萄籽提取物和0.2g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
实施例7
一种UV固化亮光树脂，按重量份数，包括以下组分525g季戊四醇三丙烯酸酯、43.7g甲基丙烯酸羟丙酯、130g丁二酸酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚、182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦和46g自产不饱和聚酯。该UV固化亮光树脂的制备方法，按以下步骤制备得到：
步骤1)：在反应釜中依次投入525g季戊四醇三丙烯酸酯、43.7g甲基丙烯酸羟丙酯、130g丁二酸酐、0.5g 2,6-二叔丁基苯酚、0.6g对羟基苯基醚，升温至40～50℃，搅拌至溶解；
步骤2)：升温至100℃并保温1～2h；
步骤3)：降温到90℃，投入182g的1,4-丁二醇二缩水甘油醚、4g三苯基膦，46g自产不饱和聚酯，缓慢升温至95℃保温1h；
步骤4)：升温至108～110℃保温；
步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温时加入0.3g番石榴籽提取物、0.1g葡萄籽提取物和0.5g桉树叶乙醇提取物，出料。
该UV固化亮光树脂不含苯环等易黄变的结构，通过简单的反应得到的改性环氧树脂具有优异的耐黄变性能，漆膜呈亮白透明。
以上内容仅仅为本发明的结构所作的举例和说明，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些显而易见的替换形式均属于本发明的保护范围。

Claims (10)

  1. 一种UV固化亮光树脂，其特征在于，按重量份数，包括以下组分：
    Figure PCTCN2020138097-appb-100001
  2. 根据权利要求1所述的UV固化亮光树脂，其特征在于，按重量份数，包括以下组分：
    Figure PCTCN2020138097-appb-100002
  3. 根据权利要求1所述的UV固化亮光树脂，其特征在于，所述羟基丙烯酸树脂为季戊四醇三丙烯酸酯与丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯，甲基丙烯酸羟丙酯中的一种或者几种的任意组合。
  4. 根据权利要求1所述的UV固化亮光树脂，其特征在于，所述酸酐为六氢苯酐或丁二酸酐中的至少一种。
  5. 根据权利要求1所述的UV固化亮光树脂，其特征在于，所述阻聚剂为对羟基苯甲醚或对苯二酚的至少一种。
  6. 根据权利要求1所述的UV固化亮光树脂，其特征在于，所述催化剂为三苯基膦、三乙胺或苄基三乙基氯化铵中的至少一种。
  7. 根据权利要求1所述的UV固化亮光树脂，其特征在于，所述抗氧剂为次磷酸、2,6-二叔丁基苯酚、苯酚中的一种或者几种的任意组合。
  8. 根据权利要求1所述的UV固化亮光树脂，其特征在于，所述环氧树脂为1,4-丁二醇二缩水甘油醚。
  9. 根据权利要求1所述的UV固化亮光树脂，其特征在于，
    所述番石榴籽提取物为多酚类物质；
    所述葡萄籽提取物为多酚类物质；
    所述桉树叶乙醇提取物按以下方法制备得到：
    (1)向盛有桉树叶的容器中加入70-80％乙醇，回流提取3次，每次1h，经100目筛过滤后，合并滤液，得桉树叶醇提取液；
    (2)加入活性炭进行脱色，将脱色后的桉树叶醇提取液经喷雾干燥，得到桉树叶乙醇提取物。
  10. 一种如权利要求1-9任一所述的UV固化亮光树脂的制备方法，其特征在于，按以下步骤进行制备：
    步骤1)：按重量份数，在反应釜中依次投入羟基丙烯酸酯、酸酐、抗氧剂和阻聚剂，升温至40～50℃，搅拌至溶解；
    步骤2)：升温至100℃并保温1～2h；
    步骤3)：降温到90℃，投入环氧树脂、催化剂和不饱和聚酯，缓慢升温至95℃保温1h；
    步骤4)：升温至108～110℃保温；
    步骤5)：测酸值，待Av≤4mgKOH/g时，降温至常温下加入番石榴籽提取物、葡萄籽提取物和桉树叶乙醇提取物，出料；
    上述合成过程通过滴定酸值和粘度控制反应程度。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5438080A (en) * 1986-05-27 1995-08-01 Nippon Oil And Fats Co., Ltd. Ultraviolet-curable coating composition
CN103497309A (zh) * 2013-10-11 2014-01-08 湖南邦弗特新材料技术有限公司 一种低成本耐黄变的uv树脂的制备方法
CN104447325A (zh) * 2014-11-12 2015-03-25 洞头县恒立印刷材料有限公司 一种可紫外光固化耐黄变环氧丙烯酸酯及其制备方法
CN109575238A (zh) * 2018-11-06 2019-04-05 江苏睿浦树脂科技有限公司 一种uv光固化环氧丙烯酸酯树脂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5438080A (en) * 1986-05-27 1995-08-01 Nippon Oil And Fats Co., Ltd. Ultraviolet-curable coating composition
CN103497309A (zh) * 2013-10-11 2014-01-08 湖南邦弗特新材料技术有限公司 一种低成本耐黄变的uv树脂的制备方法
CN104447325A (zh) * 2014-11-12 2015-03-25 洞头县恒立印刷材料有限公司 一种可紫外光固化耐黄变环氧丙烯酸酯及其制备方法
CN109575238A (zh) * 2018-11-06 2019-04-05 江苏睿浦树脂科技有限公司 一种uv光固化环氧丙烯酸酯树脂及其制备方法

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