WO2022133680A1 - 一种uv固化低粘度聚酯及其制备方法 - Google Patents

一种uv固化低粘度聚酯及其制备方法 Download PDF

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WO2022133680A1
WO2022133680A1 PCT/CN2020/138098 CN2020138098W WO2022133680A1 WO 2022133680 A1 WO2022133680 A1 WO 2022133680A1 CN 2020138098 W CN2020138098 W CN 2020138098W WO 2022133680 A1 WO2022133680 A1 WO 2022133680A1
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viscosity polyester
low
temperature
viscosity
curable low
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PCT/CN2020/138098
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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
    • 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

Definitions

  • the invention relates to the technical field of coating production, in particular to a UV-curable low-viscosity polyester 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.
  • glossy or matt paints require not only resins with bright white properties, but also properties with high hardness and low viscosity.
  • the Chinese patent with publication number CN103059717A discloses a high-leveling UV-curable coating composition for curtain coating, comprising the following components in parts by weight: 4-30 parts of low-viscosity acrylate resin, 70-96 parts of monomer, 3-8 parts of photoinitiator, 140-350 parts of solvent, and 0.01-1 part of leveling agent. Preferably: 4-20 parts of low-viscosity acrylate resin, 80-96 parts of monomer, 4-6 parts of photoinitiator, 100-250 parts of solvent, and 0.05-0.5 part of leveling agent.
  • This patent can effectively improve the leveling performance of the coating by controlling the viscosity and adding amount of the resin.
  • the coating composition prepared by this patent has yet to be verified in terms of reducing viscosity.
  • the present invention provides a UV-curable low-viscosity polyester.
  • succinic anhydride which has the advantages of small steric hindrance and small molecular weight, the lowest viscosity is only 100 mPa ⁇ s.
  • the UV-curable low-viscosity polyester makes it widely used in the field of spraying and curtain coating. It is a synthetic polyester with low-viscosity properties.
  • the present invention also provides a method for preparing the above-mentioned UV-curable low-viscosity polyester.
  • the present invention provides the following technical solutions:
  • a UV-curable low-viscosity polyester in parts by weight, comprises the following components:
  • the hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.
  • the propylene oxide is at least one of propylene oxide or epichlorohydrin.
  • 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 grape seed extract is a polyphenolic substance.
  • the grape seed extract is a class of polyphenols extracted and separated from grape seeds, and it mainly includes polyphenols such as procyanidins, 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 ethanolic extract of eucalyptus leaves 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 UV-curable low-viscosity polyester in parts by weight, includes the following components:
  • the present invention also provides a method for preparing the above-mentioned UV-cured low-viscosity polyester, which is prepared according to the following steps:
  • Step 1 in parts by weight, successively drop into hydroxy acrylate, propylene oxide, acid anhydride, polymerization inhibitor and catalyst, be warming up to 40 ⁇ 50 °C, stir to dissolve;
  • Step 2 stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3 the temperature is raised to 105-108°C, and the temperature is kept for 2h;
  • Step 4 raise the temperature to 118-120°C for 1 hour, and start sampling until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add grape seed extract and eucalyptus leaf extract at normal temperature, and discharge.
  • the UV-curable low-viscosity polyester provided by the present invention uses hydroxy acrylate and propylene oxide as main reactants to synthesize UV-curable low-viscosity polyester, and the resin is made by introducing a large amount of multifunctional hydroxy acrylate. It has high double bond density, high hardness and high gloss after curing; using succinic anhydride, an acid anhydride with small steric hindrance, small molecular weight, and molecular regularity, synthesized with a viscosity of only 100mPa ⁇ s, which can be cured by ultraviolet light. Viscosity polyester; propylene oxide brings its excellent yellowing resistance into the molecule, giving the synthesized resin excellent whitening properties.
  • the preparation method of the UV-curable low-viscosity polyester provided by the present invention is simple to operate, and can prepare UV-curable low-viscosity UV-curable low-viscosity containing unsaturated double bonds with better comprehensive properties by selecting components and adopting a temperature-programmed process. polyester.
  • a UV-curable low-viscosity polyester in parts by weight, comprises the following components:
  • the above-mentioned hydroxyacrylate is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.
  • propylene oxides are at least one of propylene oxide or epichlorohydrin.
  • the above acid anhydride is at least one of hexahydrophthalic anhydride or succinic anhydride.
  • the above-mentioned polymerization inhibitor is at least one of p-hydroxyanisole or hydroquinone.
  • the above catalyst is at least one of triphenylphosphine, triethylamine or benzyltriethylammonium chloride.
  • the above-mentioned grape seed extract is a polyphenolic substance.
  • the eucalyptus leaf ethanolic extract is prepared by the following method:
  • UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1 in parts by weight, successively drop into hydroxy acrylate, propylene oxide, acid anhydride, polymerization inhibitor and catalyst, be warming up to 40 ⁇ 50 °C, stir to dissolve;
  • Step 2 stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3 the temperature is raised to 105-108°C, and the temperature is kept for 2h;
  • Step 4 raise the temperature to 118-120°C for 1 hour, and start sampling until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add grape seed extract and eucalyptus leaf ethanol extract at room temperature, and discharge.
  • a UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1) put 348g of hydroxyethyl acrylate, 297g of epichlorohydrin, 298g of succinic anhydride, 0.54g of p-hydroxyphenyl ether and 4.7g of benzyltriethylammonium chloride into the reactor successively, and be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 2) stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3) heat up to 105-108°C and keep warm for 2h;
  • Step 4) heat up to 118-120°C for 1h, start sampling, until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add 0.3 g of grape seed extract and 2.5 g of eucalyptus leaf ethanol extract at normal temperature, and discharge.
  • a UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1) put 390g of hydroxypropyl acrylate, 297g of epichlorohydrin, 298g of succinic anhydride, 0.54g of p-hydroxyphenyl ether and 4.7g of benzyltriethylammonium chloride in the reactor successively, and be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 2) stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3) heat up to 105-108°C and keep warm for 2h;
  • Step 4) heat up to 118-120°C for 1h, start sampling, until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add 0.25g grape seed extract and 2.3g eucalyptus leaf ethanol extract at normal temperature, and discharge.
  • a UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1) successively drop in 390g of hydroxyethyl methacrylate, 297g of epichlorohydrin, 298g of succinic anhydride, 0.54g of p-hydroxyphenyl ether and 4.7g of benzyltriethylammonium chloride in the reactor, and be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 2) stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3) heat up to 105-108°C and keep warm for 2h;
  • Step 4) heat up to 118-120°C for 1h, start sampling, until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add 0.2 g of grape seed extract and 2.8 g of eucalyptus leaf ethanol extract at normal temperature, and discharge.
  • a UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1) drop in successively 432g hydroxypropyl methacrylate, 297g epichlorohydrin, 298g succinic anhydride, 0.54g p-hydroxyphenyl ether and 4.7g benzyltriethylammonium chloride in the reactor, be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 2) stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3) heat up to 105-108°C and keep warm for 2h;
  • Step 4) heat up to 118-120°C for 1h, start sampling, until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add 0.15g grape seed extract and 2.0g eucalyptus leaf ethanol extract at normal temperature, and discharge.
  • a UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1) put 348g of hydroxyethyl acrylate, 186.2g of propylene oxide, 298g of succinic anhydride, 0.54g of p-hydroxyphenyl ether and 4.7g of benzyl triethyl ammonium chloride into the reactor successively, and be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 2) stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3) heat up to 105-108°C and keep warm for 2h;
  • Step 4) heat up to 118-120°C for 1h, start sampling, until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add 0.3g grape seed extract and 3.5g eucalyptus leaf ethanol extract at normal temperature, and discharge.
  • a UV-curable low-viscosity polyester is prepared according to the following steps:
  • Step 1) put 390g of hydroxypropyl acrylate, 186.2g of propylene oxide, 298g of succinic anhydride, 0.54g of p-hydroxyphenyl ether and 4.7g of benzyl triethyl ammonium chloride into the reactor successively, and be warming up to 40 ⁇ 50°C, stir until dissolved;
  • Step 2) stop heating after heating to 80°C, and keep the temperature for 1h since the temperature rises to 95-98°C;
  • Step 3) heat up to 105-108°C and keep warm for 2h;
  • Step 4) heat up to 118-120°C for 1h, start sampling, until the acid value AV ⁇ 4mgKOH/g;
  • Step 5 reduce the temperature of the material to below 80°C, add 0.1 g of grape seed extract and 1.5 g of eucalyptus leaf ethanol extract at normal temperature, and discharge.
  • the UV-curable low-viscosity polyesters provided in Examples 2 to 7 use hydroxyacrylates and propylene oxides as main reactants to synthesize UV-curable low-viscosity polyesters, which are passed through
  • hydroxyacrylates and propylene oxides as main reactants to synthesize UV-curable low-viscosity polyesters, which are passed through
  • succinic anhydride which has small steric hindrance, small molecular weight, and molecular regularity, has the lowest viscosity.

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Abstract

提供一种UV固化低粘度聚酯，按重量份数，包括以下组分：羟基丙烯酸酯20～50份，环氧丙烷类20～45份，酸酐20～40份，阻聚剂0～0.2份，催化剂0～2份，葡萄籽提取物0.05～0.15份，桉树叶乙醇提取物0.1～0.6份。该UV固化低粘度聚酯，通过使用丁二酸酐这种具有空间位阻小和分子量小等优点的酸酐合成了粘度最低只有100mPa•s的可紫外光固化低粘度聚酯，使其广泛用于喷涂和淋涂的领域，使合成的聚酯具有低粘度性能。还提供上述UV固化低粘度聚酯的制备方法。

Description

一种UV固化低粘度聚酯及其制备方法 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固化低粘度聚酯及其制备方法。
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。
在涂料领域，亮光或哑光的油漆不仅要求树脂具有亮光白的性能，还需要有高硬度和低粘度的性能。
公开号为CN103059717A的中国专利，公开了一种淋涂用高流平性能UV固化涂料组合物，包括如下重量份数的各组分：低粘度丙烯酸酯树脂4～30份，单体70～96份，光引发剂3～8份，溶剂140～350份，流平剂0.01～1份。优选为：低粘度丙烯酸酯树脂4～20份，单体80～96份，光引发剂4～6份，溶剂100～250份，流平剂0.05～0.5份。该专利通过控制树脂的粘度和加入量，能有效提高涂料的流平性能。但该专利制备得到的涂料组合物，在降低粘度性能上仍有待验证。
因此，如何提供一种可UV固化且低粘度的聚酯，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，本发明提供了一种UV固化低粘度聚酯，通过使用丁二酸酐这种具有空间位阻小和分子量小等优点的酸酐合成了粘度最低只有100mPa·s的可紫外光固化低粘度聚酯，使其广泛用于喷涂和淋涂的领域，是合成的聚酯具有低粘度性能。本发明还提供了上述UV固化低粘度聚酯的制备方法。
为了实现上述目的，本发明提供了如下技术方案：
一种UV固化低粘度聚酯，按重量份数，包括以下组分：
Figure PCTCN2020138098-appb-000001
Figure PCTCN2020138098-appb-000002
作为本发明的技术方案的进一步描述，所述羟基丙烯酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯或甲基丙烯酸羟丙酯中的至少一种。
作为本发明的技术方案的进一步描述，所述环氧丙烷类为环氧丙烷或环氧氯丙烷中的至少一种。
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，所述葡萄籽提取物为多酚类物质。
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。
作为本发明的技术方案的进一步描述，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。
作为本发明的技术方案的进一步描述，该UV固化低粘度聚酯，按重量份数，包括以下组分：
Figure PCTCN2020138098-appb-000003
本发明还提供了上述UV固化低粘度聚酯的制备方法，按以下步骤进行制备：
(1)步骤1：按重量份数，在反应釜中依次投入羟基丙烯酸酯、环氧丙烷类、酸酐、阻聚剂和催化剂，升温至40～50℃，搅拌至溶解；
(2)步骤2：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
(3)步骤3：升温至105-108℃，保温2h；
(4)步骤4：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
(5)步骤5：将物料温度降到80℃以下，常温下加入葡萄籽提取物和桉树叶提取物，出料。
基于上述的技术方案，本发明取得的技术效果为：
(1)本发明提供的UV固化低粘度聚酯，其使用羟基丙烯酸酯和环氧丙烷类作为主体反应物，合成可UV固化的低粘度聚酯，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；使用丁二酸酐这种具有空间位阻小和分子量小，而且分子规则的酸酐合成了粘度最低只有100mPa·s的可紫外光固化低粘度聚酯；环氧丙烷将其优异的耐黄变性能带入分子中，使合成的树脂具有优异的亮白性能。
(2)本发明提供的UV固化低粘度聚酯的制备方法，操作简单，通过优选组分和采用程序升温的工艺，可制备得到综合性能较好的含有不饱和双键的可UV固化低粘度聚酯。
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固化低粘度聚酯，按重量份数，包括以下组分：
Figure PCTCN2020138098-appb-000004
上述羟基丙烯酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯或甲基丙烯酸羟丙酯中的至少一种。
上述环氧丙烷类为环氧丙烷或环氧氯丙烷中的至少一种。
上述酸酐为六氢苯酐或丁二酸酐中的至少一种。
上述阻聚剂为对羟基苯甲醚或对苯二酚的至少一种。
上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。
上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。
上述UV固化低粘度聚酯按以下步骤进行制备：
(1)步骤1：按重量份数，在反应釜中依次投入羟基丙烯酸酯、环氧丙烷类、酸酐、阻聚剂和催化剂，升温至40～50℃，搅拌至溶解；
(2)步骤2：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
(3)步骤3：升温至105-108℃，保温2h；
(4)步骤4：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
(5)步骤5：将物料温度降到80℃以下，常温下加入葡萄籽提取物和桉树叶乙醇提取物，出料。
实施例2
一种UV固化低粘度聚酯，依照以下步骤制备：
步骤1)：在反应釜中依次投入348g丙烯酸羟乙酯、297g环氧氯丙烷、298g丁二酸酐、0.54g对羟基苯基醚和4.7g苄基三乙基氯化铵，升温至40～50℃，搅拌至溶解；
步骤2)：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
步骤3)：升温至105-108℃保温2h；
步骤4)：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
步骤5)：将物料温度降到80℃以下，常温下加入0.3g葡萄籽提取物和2.5g桉树叶乙醇提取物，出料。
实施例3
一种UV固化低粘度聚酯，依照以下步骤制备：
步骤1)：在反应釜中依次投入390g丙烯酸羟丙酯、297g环氧氯丙烷、298g丁二酸酐、0.54g对羟基苯基醚和4.7g苄基三乙基氯化铵，升温至40～50℃，搅拌至溶解；
步骤2)：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
步骤3)：升温至105-108℃保温2h；
步骤4)：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
步骤5)：将物料温度降到80℃以下，常温下加入0.25g葡萄籽提取物和 2.3g桉树叶乙醇提取物，出料。
实施例4
一种UV固化低粘度聚酯，依照以下步骤制备：
步骤1)：在反应釜中依次投入390g甲基丙烯酸羟乙酯、297g环氧氯丙烷、298g丁二酸酐、0.54g对羟基苯基醚和4.7g苄基三乙基氯化铵，升温至40～50℃，搅拌至溶解；
步骤2)：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
步骤3)：升温至105-108℃保温2h；
步骤4)：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
步骤5)：将物料温度降到80℃以下，常温下加入0.2g葡萄籽提取物和2.8g桉树叶乙醇提取物，出料。
实施例5
一种UV固化低粘度聚酯，依照以下步骤制备：
步骤1)：在反应釜中依次投入432g甲基丙烯酸羟丙酯、297g环氧氯丙烷、298g丁二酸酐、0.54g对羟基苯基醚和4.7g苄基三乙基氯化铵，升温至40～50℃，搅拌至溶解；
步骤2)：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
步骤3)：升温至105-108℃保温2h；
步骤4)：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
步骤5)：将物料温度降到80℃以下，常温下加入0.15g葡萄籽提取物和2.0g桉树叶乙醇提取物，出料。
实施例6
一种UV固化低粘度聚酯，依照以下步骤制备：
步骤1)：在反应釜中依次投入348g丙烯酸羟乙酯、186.2g环氧丙烷、298g丁二酸酐、0.54g对羟基苯基醚和4.7g苄基三乙基氯化铵，升温至40～50℃，搅拌至溶解；
步骤2)：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
步骤3)：升温至105-108℃保温2h；
步骤4)：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
步骤5)：将物料温度降到80℃以下，常温下加入0.3g葡萄籽提取物和3.5g桉树叶乙醇提取物，出料。
实施例7
一种UV固化低粘度聚酯，依照以下步骤制备：
步骤1)：在反应釜中依次投入390g丙烯酸羟丙酯、186.2g环氧丙烷、298g丁二酸酐、0.54g对羟基苯基醚和4.7g苄基三乙基氯化铵，升温至40～50℃，搅拌至溶解；
步骤2)：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
步骤3)：升温至105-108℃保温2h；
步骤4)：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
步骤5)：将物料温度降到80℃以下，常温下加入0.1g葡萄籽提取物和1.5g桉树叶乙醇提取物，出料。
将实施例2-实施例7的UV固化低粘度聚酯，以及对比例1的传统的UV固化低粘度聚酯，进行检测。测试结果见表1。
表1实施例2-实施例8的UV固化低粘度聚酯，以及对比例1的传统的UV固化低粘度聚酯的性能测试表
Figure PCTCN2020138098-appb-000005
由表1的测试结果可知，实施例2-实施例7提供的UV固化低粘度聚酯，其使用羟基丙烯酸酯和环氧丙烷类作为主体反应物，合成可UV固化的低粘度聚酯，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；使用丁二酸酐这种具有空间位阻小和分子量小，而且分子规则的酸酐合成了粘度最低只有100mPa·s的可紫外光固化低粘度聚酯；环氧丙烷将其优异的耐黄变性能带入分子中，使合成的树脂具有优异的亮白性能。
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固化低粘度聚酯，其特征在于，按重量份数，包括以下组分：
    Figure PCTCN2020138098-appb-100001
  2. 根据权利要求1所述的UV固化低粘度聚酯，其特征在于，所述羟基丙烯酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯或甲基丙烯酸羟丙酯中的至少一种。
  3. 根据权利要求1所述的UV固化低粘度聚酯，其特征在于，所述环氧丙烷类为环氧丙烷或环氧氯丙烷中的至少一种。
  4. 根据权利要求1所述的UV固化低粘度聚酯，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固化低粘度聚酯，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固化低粘度聚酯，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固化低粘度聚酯，其特征在于，所述葡萄籽提取物为多酚类物质。
  8. 根据权利要求1所述的UV固化低粘度聚酯，其特征在于，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。
  9. 根据权利要求1所述的UV固化低粘度聚酯，其特征在于，按重量份数，包括以下组分：
    Figure PCTCN2020138098-appb-100002
    Figure PCTCN2020138098-appb-100003
  10. 一种如权利要求1-9任一所述的UV固化低粘度聚酯的制备方法，其特征在于，按以下步骤进行制备：
    (1)步骤1：按重量份数，在反应釜中依次投入羟基丙烯酸酯、环氧丙烷类、酸酐、阻聚剂和催化剂，升温至40～50℃，搅拌至溶解；
    (2)步骤2：加热升温到80℃后停止加热，自升温到95～98℃时，保温1h；
    (3)步骤3：升温至105-108℃，保温2h；
    (4)步骤4：升温至118-120℃保温1h，开始取样，直到测酸值AV≤4mgKOH/g；
    (5)步骤5：将物料温度降到80℃以下，常温下加入葡萄籽提取物和桉树叶提取物，出料。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028531A (zh) * 2022-07-12 2022-09-09 湖南艾硅特新材料有限公司 一种环氧环己烷甲基丙烯酸羟乙基醚、环氧环己烷丙烯酸羟乙基醚及其合成方法
CN116813891A (zh) * 2023-07-26 2023-09-29 惠州市华泓新材料股份有限公司 一种脂肪酸改性聚酯、制备方法及胶印复合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242609A (ja) * 1988-03-23 1989-09-27 Showa Highpolymer Co Ltd 紫外線硬化樹脂組成物
CN102838486A (zh) * 2012-09-25 2012-12-26 上海富臣化工有限公司 紫外光固化聚酯丙烯酸酯及其制备方法
CN110105851A (zh) * 2019-04-28 2019-08-09 英德市雅家涂料有限公司 一种低粘度快速固化的uv聚酯丙烯酸酯及其制备工艺
CN110229317A (zh) * 2019-06-13 2019-09-13 华南理工大学 高乙烯基官能度的可uv固化不饱和聚酯树脂及其制备方法与应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242609A (ja) * 1988-03-23 1989-09-27 Showa Highpolymer Co Ltd 紫外線硬化樹脂組成物
CN102838486A (zh) * 2012-09-25 2012-12-26 上海富臣化工有限公司 紫外光固化聚酯丙烯酸酯及其制备方法
CN110105851A (zh) * 2019-04-28 2019-08-09 英德市雅家涂料有限公司 一种低粘度快速固化的uv聚酯丙烯酸酯及其制备工艺
CN110229317A (zh) * 2019-06-13 2019-09-13 华南理工大学 高乙烯基官能度的可uv固化不饱和聚酯树脂及其制备方法与应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIANG ZHEN-YI, WANG JUN, CHEN YI-PING, LIN ZHAO-HUA, YANG XUE-RUI: "Study on the Ability of Scavenging Free Radical of the Different Extracts from Leaves of Eucalyptus", FOOD SCIENCE AND TECHNOLOGY, vol. 34, no. 5, 20 May 2009 (2009-05-20), pages 204 - 206, XP055946599, ISSN: 1005-9989, DOI: 10.13684/j.cnki.spkj.2009.05.067 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115028531A (zh) * 2022-07-12 2022-09-09 湖南艾硅特新材料有限公司 一种环氧环己烷甲基丙烯酸羟乙基醚、环氧环己烷丙烯酸羟乙基醚及其合成方法
CN116813891A (zh) * 2023-07-26 2023-09-29 惠州市华泓新材料股份有限公司 一种脂肪酸改性聚酯、制备方法及胶印复合物
CN116813891B (zh) * 2023-07-26 2024-04-16 惠州市华泓新材料股份有限公司 一种脂肪酸改性聚酯、制备方法及胶印复合物

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