WO2022143401A1 - 一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物 - Google Patents

一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物 Download PDF

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WO2022143401A1
WO2022143401A1 PCT/CN2021/140851 CN2021140851W WO2022143401A1 WO 2022143401 A1 WO2022143401 A1 WO 2022143401A1 CN 2021140851 W CN2021140851 W CN 2021140851W WO 2022143401 A1 WO2022143401 A1 WO 2022143401A1
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copolymer resin
carbon
epoxy
polyester resin
carbon double
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PCT/CN2021/140851
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French (fr)
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开卫华
杨雯迪
骆飚
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老虎表面技术新材料（苏州）有限公司
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Publication of WO2022143401A1 publication Critical patent/WO2022143401A1/zh

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

Definitions

  • the invention belongs to the field of copolymer resin preparation, in particular to an electron beam-curable copolymer resin, and also relates to a preparation method of the electron beam-curable copolymer resin and a powder coating composition for application thereof.
  • Electron beam curing (also known as EB curing) powder coating products is one of the main product types for the development of low temperature and fast curing technology for powder coating products, and compared with UV curing powder coating products, because electron beam curing does not require the addition of special photo-initiators The cross-linking and curing can be completed by the agent, so the electron beam curing powder coating products have better development prospects.
  • the core raw materials of electron beam-cured powder coating products include electron-beam-curable copolymer resin, and its performance also directly determines the technical level of electron beam-cured powder coating products in low-temperature rapid curing.
  • electron-beam-curable copolymer resin the core raw materials of electron beam-cured powder coating products
  • its performance also directly determines the technical level of electron beam-cured powder coating products in low-temperature rapid curing.
  • the applicant decided to develop a new electron beam-curable copolymer resin to solve the above technical problems, and to effectively promote the development process of EB-cured powder coating products to achieve mass application.
  • the object of the present invention is to provide an electron beam-curable copolymer resin and its preparation method and powder coating composition, the preparation route is simple and reliable, the raw materials are simple and easy to obtain, and the worthy copolymer resin has a relatively high content. High and stable carbon-carbon double bonds can effectively promote the development of EB-cured powder coating products for mass application.
  • An electron beam-curable copolymer resin adopts epoxy-functional methacrylate compound and polyester resin as synthetic raw materials, and the epoxy group in the epoxy-functional methacrylate compound and the carboxyl group in the polyester resin generate The reaction forms a copolymer resin with carbon-carbon double bonds; preferably, the molar ratio of epoxy groups in the epoxy-functional methacrylate compound to carboxyl groups in the polyester resin is greater than 1.
  • the epoxy functional methacrylate compound is a GMA compound.
  • the acid value of the polyester resin is not less than 60 mgKOH/g.
  • the molar ratio of epoxy groups in the epoxy-functional methacrylate compound to carboxyl groups in the polyester resin is 1.4-1.1:1.
  • its raw material also includes a catalyst for promoting the reaction.
  • the catalyst accounts for 0.1-0.5% by weight of the polyester resin.
  • the carbon-carbon double bond value in the copolymer resin is not less than 0.08mol/100g; and/or its acid value is not higher than 20mg KOH/g.
  • a kind of preparation method of the above-mentioned copolymer resin comprises the following operation steps:
  • polyester resin is dissolved by organic solvent
  • step A40) is also included, drying the reaction product after removing the solvent.
  • the target temperature range is set at 90-110°C, and the stirring time is not less than 2 hours.
  • the organic solvent adopts methyl isobutyl ketone and/or butyl acetate.
  • an electron beam curable powder coating composition the raw material of which comprises the copolymer resin as described above.
  • the acid value data detection standard involved in this application is based on ISO 3682-1998; the full name of GMA involved is Glycidyl Methacrylate, which in Chinese means glycidyl methacrylate, which belongs to a well-known type of acrylic resin; The MDF involved is the abbreviation of Medium Density Fiberboard, which means: Medium Density Fiberboard.
  • the application also specially sets the following test method for the carbon-carbon double bond value:
  • tribromo compound methanol solution Weigh 25.33g of anhydrous sodium bromide (dried at 130°C for 3h), dissolve it in 333.3mL of methanol, add 1.7mL of bromine, and store in a brown wide-mouth bottle , wait for uniformity, and use after 24 hours.
  • 0.5 wt% starch indicator Weigh 0.5 g of soluble starch and adjust it to a paste state with 5 mL of deionized water. Then poured into 95mL of boiling water, slightly boiled for 2min. Cool and take the upper clear liquid for use.
  • the amount of carbon-carbon double bonds contained in 100g of resin is defined as the carbon-carbon double bond value, and the carbon-carbon double bond value is calculated as follows:
  • V 0 volume of standard sodium thiosulfate solution consumed by blank group (mL);
  • V 1 volume of standard sodium thiosulfate solution consumed by titration sample (mL);
  • C B concentration of standard sodium thiosulfate solution (mol /L);
  • m weighed resin mass (g).
  • the technical route of the present application is that the epoxy group in the epoxy functional methacrylate compound reacts with the carboxyl group in the polyester resin to form a copolymer resin with carbon-carbon double bonds, the preparation route is simple and reliable, and the raw materials are simple and easy to obtain,
  • the prepared copolymer resin has relatively high and stable carbon-carbon double bonds, and the present application also specifically makes the molar ratio of the epoxy group in the epoxy functional methacrylate compound to the carboxyl group in the polyester resin greater than 1.
  • This can significantly improve the carbon-carbon double bond content and its stability in the copolymer resin, this feature can significantly improve the low-temperature curing performance of the powder coating composition it is applied to, and can effectively promote EB curing powder coating products to achieve batch production.
  • Application development process is that the epoxy group in the epoxy functional methacrylate compound reacts with the carboxyl group in the polyester resin to form a copolymer resin with carbon-carbon double bonds, the preparation route is simple and reliable, and the raw materials are simple and easy to obtain
  • This example proposes an electron beam-curable copolymer resin, using epoxy-functional methacrylate compound and polyester resin as synthetic raw materials, through the epoxy group in the epoxy-functional methacrylate compound and polyester
  • the carboxyl groups in the resin react to form a copolymer resin with carbon-carbon double bonds; wherein preferably, the molar ratio of epoxy groups in the epoxy-functional methacrylate compound to carboxyl groups in the polyester resin is greater than 1, more preferably 1.4 -1.1:1.
  • the epoxy-functional methacrylate compound adopts GMA compound, of course, other epoxy-functional methacrylate compounds with epoxy groups can also be selected, which are not particularly limited in this embodiment;
  • the acid value of the polyester resin is not less than 60mgKOH/g, more preferably 65-100mgKOH/g, which is beneficial to improve the reactivity between it and epoxy groups.
  • the specific type of polyester resin The specific selection may be made according to the actual situation, and this embodiment does not make a unique limitation.
  • the raw material also includes a catalyst for promoting the reaction.
  • the preferred catalyst can be a phosphine-based catalyst (which can be directly purchased from the market, or can be configured as a masterbatch by itself), or other known catalysts with similar effects can be used. , this embodiment does not limit it exclusively; further preferably, the catalyst accounts for 0.1-0.5 wt % of the polyester resin by weight, more preferably 0.2-0.4 wt %.
  • the present embodiment also proposes a preparation method of the above-mentioned copolymer resin, and the synthesis process includes the following operation steps:
  • polyester resin for example, it can be 200-400g
  • organic solvent preferably, methyl isobutyl ketone and/or butyl acetate are used as the organic solvent, and of course, it is also possible to Select other suitable organic solvent, as long as it can achieve effective solvent for polyester resin;
  • the raw material is stirred at the target temperature, so that the epoxy group in the epoxy functional methacrylate compound reacts with the carboxyl group in the polyester resin to form a copolymer resin reaction product with carbon-carbon double bonds; wherein preferably Ground, the target temperature range is set at 90-110 °C (the temperature is too low to be unfavorable for the reaction to proceed, and the temperature is too high will make the reaction product appear gelatinous), the stirring time is not less than 2 hours, preferably not less than 4 hours, More preferably, it is 4-8 hours, and more preferably 6-8 hours, which is favorable for sufficient reaction.
  • step A40) is also included, drying the reaction product after removing the solvent.
  • the carbon-carbon double bond value in the copolymer resin obtained in this embodiment can be stably maintained at not less than 0.08mol/100g, which represents a high carbon-carbon double bond content; and/or its acid value is not higher than 20mg KOH/g, which means that the carboxyl group in the polyester resin raw material participates in the synthesis reaction more completely.
  • an electron beam curable powder coating composition the raw material of which includes the above copolymer resin
  • the copolymer resin provided in this embodiment is mixed with an appropriate ratio of pigments, fillers and/or additives. It can be obtained after mixing, wherein, the weight ratio of the copolymer resin can be selected at 35-95 wt%, and the mixing process can adopt the known process of powder coating composition, and can specifically preferably include weighing, premixing, melt extrusion, grinding. Powder, cyclone separation and other processes. Of course, other well-known preparation processes can also be used to obtain the powder coating composition of this embodiment, and the preparation process thereof is not particularly limited in this application.
  • Embodiment 1 a kind of copolymer resin that can be cured by electron beam, and its synthesis process comprises the following operation steps:
  • the raw material is stirred at the target temperature of 100 ° C, and the stirring time is 6 hours, so that the epoxy group in the GMA compound reacts with the carboxyl group in the polyester resin to form a copolymer resin reaction product with carbon-carbon double bonds ;
  • the obtained copolymer resin is poured into a tetrafluoroethylene watch glass for vacuum drying to obtain an electron beam-curable copolymer resin product.
  • the carbon-carbon double bond value thereof is all about 0.089mol/100g, and its acid value is not higher than 20mg KOH/g.
  • Embodiment 2 the remaining technical solutions of this embodiment 2 are the same as those of embodiment 1, the difference is that in this embodiment 2, in its step A20), the molar ratio of epoxy group in the GMA compound to the carboxyl group in the polyester resin is 1.1: 1.
  • Embodiment 3 The remaining technical solutions of this embodiment 3 are the same as those of embodiment 1, the difference is that in this embodiment 3, in its step A20), the molar ratio of epoxy group in the GMA compound to the carboxyl group in the polyester resin is 1.3: 1.
  • the carbon-carbon double bond value is 0.089mol/100g, and the acid value is not higher than 20mg KOH/g.
  • Embodiment 4 the remaining technical solutions of this embodiment 4 are the same as those of embodiment 1, the difference is that in this embodiment 4, in its step A20), the molar ratio of epoxy group in the GMA compound to the carboxyl group in the polyester resin is 1: 1.
  • Embodiment 5 The remaining technical solutions of this embodiment 5 are the same as those of embodiment 1, except that in this embodiment 5, in its step A20), the molar ratio of epoxy group in the GMA compound to the carboxyl group in the polyester resin is 0.9: 1.
  • the carbon-carbon double bond value is 0.072mol/100g, and the acid value is not higher than 20mg KOH/g.
  • Embodiment 6 The remaining technical solutions of this embodiment 6 are the same as those of embodiment 1, except that no catalyst is added in step A20) of this embodiment 6.
  • the carbon-carbon double bond value is 0.081mol/100g, and the acid value is not higher than 20mg KOH/g.
  • Embodiment 7 The remaining technical solutions of Embodiment 7 are the same as those of Embodiment 1, except that in Step A30) of Embodiment 7, the target temperature is set to 90°C. After the finished product of the copolymer resin obtained in Example 7 is tested for the carbon-carbon double bond value, the carbon-carbon double bond value is 0.088mol/100g, and the acid value is not higher than 20mg KOH/g.
  • Embodiment 8 The remaining technical solutions of Embodiment 8 are the same as those of Embodiment 1, except that in Step A30) of Embodiment 8, the target temperature is set to 110°C. After the finished product of the copolymer resin obtained in Example 8 is tested for the carbon-carbon double bond value, the carbon-carbon double bond value is 0.090mol/100g, and the acid value is not higher than 20mg KOH/g.
  • Embodiment 9 The remaining technical solutions of Embodiment 9 are the same as those of Embodiment 1, except that in Step A30) of Embodiment 9, the target temperature is set to 120°C. After the finished product of the copolymer resin obtained in Example 9 is tested for carbon-carbon double bond value respectively, its carbon-carbon double bond value is 0.091mol/100g, and its acid value is not higher than 20mg KOH/g.
  • Embodiment 10 The remaining technical solutions of this embodiment 10 are the same as those of embodiment 1, the difference is that in this embodiment 10 in its step A20), the molar ratio of epoxy group in the GMA compound to the carboxyl group in the polyester resin is 0.85: 1.
  • the carbon-carbon double bond value is 0.06mol/100g, and the acid value is higher than 20mg KOH/g.
  • Embodiment 11 The remaining technical solutions of this embodiment 11 are the same as those of embodiment 1, except that in this embodiment 11, in its step A20), the molar ratio of epoxy group in the GMA compound to the carboxyl group in the polyester resin is 0.8: 1.
  • the carbon-carbon double bond value is 0.04mol/100g, and its acid value is greater than 20mg KOH/g.
  • Embodiment 12 The remaining technical solutions of this embodiment 12 are the same as those of embodiment 1, except that this embodiment 12 adopts polyester resin TM5013 from Zhejiang Chuanhua Tiansong to replace SJ3B of Anhui Shenjian in embodiment 1.
  • the carbon-carbon double bond value was 0.088mol/100g, and the acid value was less than 20mg KOH/g.
  • Embodiment 13 The remaining technical solutions of this embodiment 13 are the same as those of embodiment 1, except that this embodiment 13 adopts Crylcoat 2671-3 from ALLNEX (acid value range is 40-50 mgKOH/g) to replace the Anhui in embodiment 1 Excalibur's SJ3B.
  • the carbon-carbon double bond value was 0.078mol/100g, and the acid value was less than 20mg KOH/g.
  • Embodiment 14 The remaining technical solutions of Embodiment 14 are the same as those of Embodiment 1, except that in Step A30) of Embodiment 14, the target temperature is set to 80°C.
  • the carbon-carbon double bond value was 0.071mol/100g, and the acid value was higher than 20mg KOH/g.
  • Embodiment 15 The remaining technical solutions of this embodiment 15 are the same as those of embodiment 1, the difference is that in the step A30) of this embodiment 15, the stirring time is 4 hours.
  • the carbon-carbon double bond value is 0.08mol/100g, and the acid value is not higher than 20mg KOH/g.
  • Embodiment 16 The remaining technical solutions of this embodiment 16 are the same as those of embodiment 1, the difference is that in the step A30) of this embodiment 16, the stirring time is 3 hours.
  • the carbon-carbon double bond value was 0.065mol/100g, and the acid value was higher than 20mg KOH/g.
  • the layer thickness can be selected according to actual needs.
  • the recommended coating thickness range is 100-180 ⁇ m (test standard is based on ISO 2360-2017).
  • the finished copolymer resin products obtained in Examples 2-16 are respectively used as the raw materials of the powder coating composition in place of the raw materials of the finished copolymer resin products obtained in Example 1.
  • substrate, spraying and EB After the curing process, the substrate coatings corresponding to Examples 2-16 were obtained respectively. After the basic performance tests shown in Table 1 above were performed on these substrate coatings, it was found that Examples 2, 3, 4, 6, and 7 , 8, 9, 12, and 15 achieved similar technical effects as Example 1, and Examples 5, 10, 11, 13, 14, and 16 performed poorly, and Example 11 had the worst performance in basic performance.

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Abstract

本发明公开了一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物，采用环氧官能甲基丙烯酸酯化合物以及聚酯树脂作为合成原料，通过环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂；本发明的制备路线简单可靠且原料简单易于取得，所值得的共聚物树脂中具有含量较高且稳定的碳碳双键，可有效推进EB固化粉末涂料产品实现批量应用的发展进程。

Description

一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物
本申请要求于2020年12月29日提交中国国家知识产权局专利局，申请号为“2020115995817”、发明名称为“一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物”的中国专利申请优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于共聚物树脂制备领域，具体涉及一种可电子束固化的共聚物树脂，本发明还涉及了该可电子束固化的共聚物树脂的制备方法及其应用的粉末涂料组合物。
背景技术
电子束固化(也称为EB固化)粉末涂料产品是粉末涂料产品发展低温快速固化技术方向的主要产品类型之一，而且相对于UV固化粉末涂料产品，由于电子束固化不需要添加专用的光引发剂即可完成交联固化，因此电子束固化粉末涂料产品具有更好的发展前景。
进一步来说，电子束固化粉末涂料产品的核心原料包括可电子束固化的共聚物树脂，其性能表现也直接决定了电子束固化粉末涂料产品在低温快速固化上的技术水平。然而现有技术中，仅有一些关于可电子束固化的共聚物树脂理论合成方法的相关信息，市场上也难以购买到商业化的可电子束固化的共聚物树脂，即便购买得到，不仅成本昂贵，而且经本申请人进行测试，其碳碳双键值不高于0.06mol/100g，且每次检测后的差异值也较大，因而可知其碳碳双键官能团的含量较低而且其稳定性较差，由于碳碳双键官能团是实现电子束固化性能的特征官能团，该较差性能指标会直接导致其应用在粉末涂料产品中后的低温快速固化性能一般，难以进行规模推广应用。
为此，本申请人决定开发新可电子束固化的共聚物树脂来对以上技术问题，来有效推进EB固化粉末涂料产品实现批量应用的发展进程。
发明内容
有鉴于此，本发明的目的在于提供一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物，制备路线简单可靠且原料简单易于取得，所值得的共聚物树脂中具有含量较高且稳定的碳碳双键，可有效推进EB固化粉末涂料产品实现批量应用的发展进程。
本发明采用的技术方案如下：
一种可电子束固化的共聚物树脂，采用环氧官能甲基丙烯酸酯化合物以及聚酯树脂作为合成原料，通过环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂；优选地，所述环氧官能甲基丙烯酸酯化合物中环氧基与所述聚酯树脂中羧基的投料摩尔比例大于1。
优选地，所述环氧官能甲基丙烯酸酯化合物采用GMA化合物。
优选地，所述聚酯树脂的酸值不低于60mgKOH/g。
优选地，所述环氧官能甲基丙烯酸酯化合物中环氧基与所述聚酯树脂中羧基的投料摩尔比例为1.4-1.1：1。
优选地，其原料还包括用于促进反应的催化剂。
优选地，所述催化剂占所述聚酯树脂重量份比例的0.1-0.5wt％。
优选地，所述共聚物树脂中的碳碳双键值不小于0.08mol/100g；和/或其酸值不高于20mg KOH/g。
优选地，一种如上所述共聚物树脂的制备方法，其合成工艺包括如下操作步骤：
A10)、将聚酯树脂通过有机溶剂进行溶解；
A20)、在惰性气体保护环境下，向溶解后的聚酯树脂添加环氧官能甲基 丙烯酸酯化合物；
A30)、在目标温度下对原料进行搅拌，使得环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂反应产物。
优选地，还包括步骤A40)、将反应产物中的溶剂去除后进行干燥。
优选地，将所述目标温度范围设置在90-110℃，搅拌时间不低于2小时。
优选地，所述有机溶剂采用甲基异丁酮和/或乙酸丁酯。
优选地，一种可电子束固化的粉末涂料组合物，其原料包括如上所述的共聚物树脂。
需要说明的是，本申请涉及的酸值数据检测标准依据是ISO 3682-1998；涉及的GMA的全称为Glycidyl Methacrylate，中文意思是指甲基丙烯酸缩水甘油酯，属于一种公知类型的丙烯酸树脂；涉及的MDF是Medium Density Fiberboard的缩写，其中文意思是指：中密度纤维板。
为了验证共聚物树脂中的碳碳双键值含量，本申请还特别设置了如下碳碳双键值的测试方法：
S1、预先配置如下溶液
(1).0.1mol/L三溴化合物甲醇溶液：称取25.33g无水溴化钠(130℃干燥3h)溶于333.3mL的甲醇中，加入1.7mL的溴，储存在棕色的广口瓶中，待均匀，过24小时后使用。
(2).10wt％碘化钾(KI)溶液：称取10g KI溶于水中，用棕色容量瓶定量至100mL并储存备用。
(3).0.5wt％的淀粉指示剂：称取0.5g可溶性淀粉，用5mL的去离子水调至浆糊状。然后倒入95mL的煮沸的水中，微沸2min。冷却取上层澄清液体使用。
S2、碳碳双键值测定
称取适量(可为0.2-0.4g)共聚物树脂样品于锥形瓶中，加入20mL三氯甲烷有机溶剂，充分震荡使共聚物树脂溶解，用移液管加入10mL三溴化合物甲醇溶液，暗处放置1h。加入5mL的10wt％碘化钾溶液，充分震荡，以硫代硫酸钠标准溶液进行滴定，滴至溶液呈黄色时加入5mL 0.5wt％的淀粉指示剂，继续滴定至蓝色消失即是终点，消耗硫代硫酸钠的体积记为V 1。同时做空白实验，消耗硫代硫酸钠的体积记为V 0。
S3、计算
把100g树脂中含有的碳碳双键的物质的量定义为碳碳双键值，碳碳双键值按下式计算：
Figure PCTCN2021140851-appb-000001
其中，V 0＝空白组消耗标准硫代硫酸钠溶液的体积(mL)；V 1＝滴定样品消耗标准硫代硫酸钠溶液的体积(mL)；C B＝硫代硫酸钠标准溶液浓度(mol/L)；m＝称取树脂的质量(g)。
本申请的技术路线是通过环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂，制备路线简单可靠且原料简单易于取得，所制得的共聚物树脂中具有含量较高且稳定的碳碳双键，本申请还特别将环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基的投料摩尔比例大于1，申请人发现这可以明显提高共聚物树脂中的碳碳双键含量及其稳定性，该特征可以显著提高其应用粉末涂料组合物的低温固化性能，可有效推进EB固化粉末涂料产品实现批量应用的发展进程。
具体实施方式
本实施例提出了一种可电子束固化的共聚物树脂，采用环氧官能甲基丙烯酸酯化合物以及聚酯树脂作为合成原料，通过环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树 脂；其中优选地，环氧官能甲基丙烯酸酯化合物中环氧基与聚酯树脂中羧基的投料摩尔比例大于1，更优选为1.4-1.1：1。
优选地，在本实施方式中，环氧官能甲基丙烯酸酯化合物采用GMA化合物，当然也可以选用其他具有环氧基的环氧官能甲基丙烯酸酯化合物，本实施例对其不做特别限制；优选地，在本实施方式中，聚酯树脂的酸值不低于60mgKOH/g，更优选为65-100mgKOH/g，利于提高其与环氧基之间的反应活性，聚酯树脂的具体型号可以根据实际情况进行具体选择，本实施例不做唯一限定。
优选地，其原料还包括用于促进反应的催化剂，优选的催化剂可以采用膦系催化剂(可以从市场上直接采购得到，也可以自己配置成母料)，也可以采用其他具有类似效果的公知催化剂，本实施例对其不做唯一限定；进一步优选地，催化剂占聚酯树脂重量份比例的0.1-0.5wt％，更优选为0.2-0.4wt％。
优选地，本实施例还提出了一种如上所述共聚物树脂的制备方法，其合成工艺包括如下操作步骤：
A10)、称取适量聚酯树脂(例如可为200-400g)，将该聚酯树脂通过有机溶剂进行溶解；优选地，有机溶剂采用甲基异丁酮和/或乙酸丁酯，当然也可以选用其他合适的有机溶剂，只要能实现对聚酯树脂的有效溶剂即可；
A20)、在惰性气体保护环境下，向溶解后的聚酯树脂添加环氧官能甲基丙烯酸酯化合物；
A30)、在目标温度下对原料进行搅拌，使得环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂反应产物；其中优选地，将目标温度范围设置在90-110℃(温度过低不利于反应的进行，温度过高会使得反应产物出现凝胶状)，搅拌时间不低于2小时，优选不低于4小时，进一步优选为4-8小时，更优选为6-8小时，利于进行充分反应。
优选地，还包括步骤A40)、将反应产物中的溶剂去除后进行干燥。
优选地，经过测试，本实施例所获得共聚物树脂中的碳碳双键值可以稳定保持在不小于0.08mol/100g，代表具有高碳碳双键含量；和/或其酸值不高于20mg KOH/g，代表聚酯树脂原料中的羧基基团较完全地参与了合成反应。
优选地，一种可电子束固化的粉末涂料组合物，其原料包括如上的共聚物树脂，本申请在实际实施时，将本实施例提供的共聚物树脂与合适比例的颜填料和/助剂混合后即可得到，其中，共聚物树脂的重量份比例可以选择在35-95wt％，混合工艺可以采用粉末涂料组合物的公知工艺，可具体优选包括称量、预混、熔融挤出、磨粉、旋风分离等工序。当然也可以采用其他公知制备工艺来得到本实施例的粉末涂料组合物，本申请对其制备工艺没有特别限定之处。
为了验证本申请实施时的技术效果，本申请特别展开了以下多组实施例用于说明本申请中共聚物树脂的具体制备过程：
实施例1：一种可电子束固化的共聚物树脂，其合成工艺包括如下操作步骤：
A10)、称取240g聚酯树脂(具体选用来自安徽神剑的SJ3B)，并通过300mL甲基异丁酮进行溶解，为了实现对聚酯树脂的快速完全溶解，在溶解过程中可进行40℃温度下加热并同时施加搅拌；
A20)、在氮气惰性气体保护环境下，向溶解后的聚酯树脂添加来自Macklin提供的商业化GMA化合物以及0.72g(占聚酯树脂重量份比例为0.3wt％)的膦系催化剂(具体选用来自阿科玛的Reafree C4705-10)，其中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为1.2：1；
A30)、在100℃的目标温度下对原料进行搅拌，搅拌时间为6小时，使得GMA化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂反应产物；
A40)、通过旋蒸仪将反应产物中的溶剂旋蒸去除后，将所得的共聚物树脂倒入四氟乙烯表面皿中进行真空干燥，即可得到可电子束固化的共聚物树脂成品。
本实施例1所获得共聚物树脂成品经过分别三次碳碳双键值测试后，其碳碳双键值均约为0.089mol/100g，且其酸值不高于20mg KOH/g。
实施例2：本实施例2的其余技术方案同实施例1，区别在于，本实施例2在其步骤A20)中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为1.1：1。
本实施例2所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.087mol/100g，且其酸值不高于20mg KOH/g。
实施例3：本实施例3的其余技术方案同实施例1，区别在于，本实施例3在其步骤A20)中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为1.3：1。
本实施例3所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.089mol/100g，且其酸值不高于20mg KOH/g。
实施例4：本实施例4的其余技术方案同实施例1，区别在于，本实施例4在其步骤A20)中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为1：1。
本实施例4所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.082mol/100g，且其酸值不高于20mg KOH/g。
实施例5：本实施例5的其余技术方案同实施例1，区别在于，本实施例5在其步骤A20)中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为0.9：1。
本实施例5所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.072mol/100g，且其酸值不高于20mg KOH/g。
实施例6：本实施例6的其余技术方案同实施例1，区别在于，本实施例6在其步骤A20)中没有添加催化剂。
本实施例6所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.081mol/100g，且其酸值不高于20mg KOH/g。
实施例7：本实施例7的其余技术方案同实施例1，区别在于，本实施例7在其步骤A30)中，目标温度设置为90℃。本实施例7所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.088mol/100g，且其酸值不高于20mg KOH/g。
实施例8：本实施例8的其余技术方案同实施例1，区别在于，本实施例8在其步骤A30)中，目标温度设置为110℃。本实施例8所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.090mol/100g，且其酸值不高于20mg KOH/g。
实施例9：本实施例9的其余技术方案同实施例1，区别在于，本实施例9在其步骤A30)中，目标温度设置为120℃。本实施例9所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.091mol/100g，且其酸值不高于20mg KOH/g。
实施例10：本实施例10的其余技术方案同实施例1，区别在于，本实施例10在其步骤A20)中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为0.85：1。
本实施例10所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.06mol/100g，且其酸值高于20mg KOH/g。
实施例11：本实施例11的其余技术方案同实施例1，区别在于，本实施例11在其步骤A20)中，GMA化合物中环氧基与聚酯树脂中羧基的投料摩尔比例为0.8：1。
本实施例11所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳 双键值为0.04mol/100g，且其酸值大于20mg KOH/g。
实施例12：本实施例12的其余技术方案同实施例1，区别在于，本实施例12采用来自浙江传化天松的聚酯树脂TM5013替代实施例1中的安徽神剑的SJ3B。
本实施例12所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.088mol/100g，且其酸值小于20mg KOH/g。
实施例13：本实施例13的其余技术方案同实施例1，区别在于，本实施例13采用来自ALLNEX的Crylcoat 2671-3(酸值范围为40-50mgKOH/g)替代实施例1中的安徽神剑的SJ3B。
本实施例13所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.078mol/100g，且其酸值小于20mg KOH/g。
实施例14：本实施例14的其余技术方案同实施例1，区别在于，本实施例14在其步骤A30)中，目标温度设置为80℃。
本实施例14所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.071mol/100g，且其酸值高于20mg KOH/g。
实施例15：本实施例15的其余技术方案同实施例1，区别在于，本实施例15在其步骤A30)中，搅拌时间为4小时。
本实施例15所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.08mol/100g，且其酸值不高于20mg KOH/g。
实施例16：本实施例16的其余技术方案同实施例1，区别在于，本实施例16在其步骤A30)中，搅拌时间为3小时。
本实施例16所获得共聚物树脂成品经过分别碳碳双键值测试后，其碳碳双键值为0.065mol/100g，且其酸值高于20mg KOH/g。
本申请以75wt％的实施例1制得的共聚物树脂成品、0.5wt％的流平剂(市场上直接采购得到的公知流平剂)、0.5wt％的安息香以及24wt％的填料硫酸 钡作为粉末涂料组合物的配方原料，然后经过称量、预混、熔融挤出、磨粉、旋风分离工序制备得到粉末涂料组合物；然后以MDF作为基材，将本申请提供的粉末涂料组合物向MDF基材喷涂该粉末涂料组合物后进行EB固化成型得到固化涂层，其中，所采用的EB固化的工艺条件为：将粉末涂料组合物预先在110-120℃温度下(红外加热方式)预热2-3分钟，使其处于熔融状态，然后通过EB固化设备对熔融状态的涂膜进行EB固化，该EB固化的能量为50-300keV，剂量为10-120kGy；本实施例1的固化涂层厚度可以根据实际需要进行具体选择，建议的涂层厚度范围为100-180μm(测试标准依据为：ISO 2360-2017)。
本申请对以上固化涂层进行了如下基本性能测试，测试结果如下表1：
表1 固化涂层的基本性能测试
  测试标准 测试结果
划格测试 ISO 2409-2013 0级Grade
杯突测试(5mm) ISO 1520-2006 通过Pass
弯曲测试(5mm) ISO 1519-2011 通过Pass
冲击测试(20inch/bs) ISO6272-1-2011 通过Pass
UVB500小时后的保光率 ASTM G154-2016 ≥90％
本申请分别将实施例2-16得到的共聚物树脂成品分别替代实施例1制得的共聚物树脂成品原料应用作为粉末涂料组合物的配方原料，通过相同的制备方法、基材、喷涂以及EB固化工艺后，分别得到了实施例2-16对应的基材涂层，对这些基材涂层进行了如上表1所示的基本性能测试后，发现实施例2、3、4、6、7、8、9、12以及15取得了与实施例1类似的技术效果，实施例5、10、11、13、14以及16的表现较差，其中实施例11的基本性能表现最差。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实 现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (13)

  1. 一种可电子束固化的共聚物树脂，其特征在于，采用环氧官能甲基丙烯酸酯化合物以及聚酯树脂作为合成原料，通过环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂。
  2. 根据权利要求1所述的共聚物树脂，其特征在于，所述环氧官能甲基丙烯酸酯化合物中环氧基与所述聚酯树脂中羧基的投料摩尔比例大于1。
  3. 根据权利要求1所述的共聚物树脂，其特征在于，所述环氧官能甲基丙烯酸酯化合物采用GMA化合物。
  4. 根据权利要求1所述的共聚物树脂，其特征在于，所述聚酯树脂的酸值不低于60mgKOH/g。
  5. 根据权利要求1所述的共聚物树脂，其特征在于，所述环氧官能甲基丙烯酸酯化合物中环氧基与所述聚酯树脂中羧基的投料摩尔比例为1.4-1.1：1。
  6. 根据权利要求1所述的共聚物树脂，其特征在于，其原料还包括用于促进反应的催化剂。
  7. 根据权利要求6所述的共聚物树脂，其特征在于，所述催化剂占所述聚酯树脂重量份比例的0.1-0.5wt％。
  8. 根据权利要求1所述的共聚物树脂，其特征在于，所述共聚物树脂中的碳碳双键值不小于0.08mol/100g；和/或其酸值不高于20mg KOH/g。
  9. 一种如权利要求1-8之一所述共聚物树脂的制备方法，其特征在于，其合成工艺包括如下操作步骤：
    A10)、将聚酯树脂通过有机溶剂进行溶解；
    A20)、在惰性气体保护环境下，向溶解后的聚酯树脂添加环氧官能甲基丙烯酸酯化合物；
    A30)、在目标温度下对原料进行搅拌，使得环氧官能甲基丙烯酸酯化合物中的环氧基与聚酯树脂中的羧基发生反应形成具有碳碳双键的共聚物树脂反应产物。
  10. 根据权利要求9所述的制备方法，其特征在于，还包括步骤A40)、将反应产物中的溶剂去除后进行干燥。
  11. 根据权利要求9所述的制备方法，其特征在于，将所述目标温度范围设置在90-110℃，搅拌时间不低于2小时。
  12. 根据权利要求9所述的制备方法，其特征在于，所述有机溶剂采用甲基异丁酮和/或乙酸丁酯。
  13. 一种可电子束固化的粉末涂料组合物，其特征在于，其原料包括如权利要求1-8之一所述的共聚物树脂。
PCT/CN2021/140851 2020-12-29 2021-12-23 一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物 WO2022143401A1 (zh)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5639560A (en) * 1995-04-26 1997-06-17 U C B S.A. Powder composition of crystalline polyesters containing end methacrylyl groups
CN1398285A (zh) * 2000-02-09 2003-02-19 Ucb公司 可由辐射固化的粉末组合物
CN1950468A (zh) * 2004-05-07 2007-04-18 氰特表面技术有限公司 辐射固化性低光泽粉末涂料组合物
CN102597053A (zh) * 2009-11-13 2012-07-18 氰特表面技术有限公司 用于涂料的聚酯
WO2012150300A1 (en) * 2011-05-05 2012-11-08 Cytec Surface Specialties, S.A. Process for producing polyesters
CN112745494A (zh) * 2020-12-29 2021-05-04 老虎表面技术新材料（苏州）有限公司 一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669962B (zh) * 2016-03-16 2018-01-12 无锡海特圣大光电材料科技有限公司 一种紫外光固化粉末涂料用树脂的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5639560A (en) * 1995-04-26 1997-06-17 U C B S.A. Powder composition of crystalline polyesters containing end methacrylyl groups
CN1398285A (zh) * 2000-02-09 2003-02-19 Ucb公司 可由辐射固化的粉末组合物
CN1950468A (zh) * 2004-05-07 2007-04-18 氰特表面技术有限公司 辐射固化性低光泽粉末涂料组合物
CN102597053A (zh) * 2009-11-13 2012-07-18 氰特表面技术有限公司 用于涂料的聚酯
WO2012150300A1 (en) * 2011-05-05 2012-11-08 Cytec Surface Specialties, S.A. Process for producing polyesters
CN112745494A (zh) * 2020-12-29 2021-05-04 老虎表面技术新材料（苏州）有限公司 一种可电子束固化的共聚物树脂及其制备方法和粉末涂料组合物

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