WO2021109731A1 - 一种自乳化环氧树脂乳液及其制备方法和应用 - Google Patents

一种自乳化环氧树脂乳液及其制备方法和应用 Download PDF

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WO2021109731A1
WO2021109731A1 PCT/CN2020/121847 CN2020121847W WO2021109731A1 WO 2021109731 A1 WO2021109731 A1 WO 2021109731A1 CN 2020121847 W CN2020121847 W CN 2020121847W WO 2021109731 A1 WO2021109731 A1 WO 2021109731A1
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epoxy resin
self
parts
polyoxyethylene ether
resin emulsion
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PCT/CN2020/121847
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French (fr)
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潘德忠
张春琪
张超
徐庆华
吴斌
崔巍巍
邓伟
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苏州太湖电工新材料股份有限公司
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Publication of WO2021109731A1 publication Critical patent/WO2021109731A1/zh

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the technical field of water-based coatings, and specifically relates to a self-emulsifying epoxy resin emulsion and a preparation method and application thereof.
  • Epoxy resin is widely used in various industries such as construction, woodware, hardware, electronics and electrical appliances because of its good bonding performance, high mechanical strength and low curing shrinkage.
  • Traditional epoxy resin coatings use organic solvents as diluents, causing direct damage to the environment and the physical and mental health of coating workers. As environmental protection requirements are getting higher and higher, traditional epoxy resin coatings can no longer meet, and there is an urgent need to propose sustainable development solutions.
  • Epoxy emulsion uses water as solvent, which overcomes the VOC problem caused by traditional epoxy coatings due to organic solvents. At the same time, it also maintains the performance of the original coatings, and has excellent economic value and application value.
  • most of the epoxy emulsions currently have some problems: (1) Poor storage stability; (2) Higher cured film hardness and poor flexibility, the paint film is easy to crack; (3) The need to add a co-solvent can not achieve completely zero VOC Discharge; (4) Poor anti-corrosion performance and easy rust, which restrict the use of water-based epoxy emulsion.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a new type of self-emulsifying epoxy resin emulsion, which can self-emulsify into a uniform and stable emulsion without adding a co-solvent, with a long storage period, and truly realize Zero VOC emission; At the same time, it has excellent film toughness and anti-rust performance after film formation.
  • the invention also provides a preparation method of the self-emulsifying epoxy resin emulsion.
  • the invention also provides an epoxy coating containing the self-emulsifying epoxy resin emulsion.
  • the present invention adopts the following technical solutions:
  • a self-emulsifying epoxy resin emulsion the raw materials of which include epoxy resin and water, and the raw materials also include sorbitan polyoxyethylene ether fatty acid ester, fatty alcohol polyether phosphate and amine accelerator; in parts by mass In count, among the raw materials, 100-150 parts of epoxy resin, 10-20 parts of sorbitan polyoxyethylene ether fatty acid ester, 10-20 parts of fatty alcohol polyether phosphate, 1-5 parts of amine accelerator Parts and 100-10000 parts of water; wherein the feed mass ratio of the sorbitan polyoxyethylene ether fatty acid ester to the epoxy resin is 0.075-0.180:1, and the fatty alcohol polyether phosphate is The feed mass ratio of the epoxy resin is 0.07-0.20:1.
  • the polyoxyethylene sorbitan fatty acid ester is selected from one or a combination of Tween 20, Tween 60 and Tween 80.
  • the fatty alcohol polyether phosphate is selected from the group consisting of laureth polyoxyethylene ether phosphate, isooctyl alcohol polyoxyethylene ether phosphate, and iso-tridecanol polyoxyethylene ether One or more combinations of phosphate esters.
  • the self-emulsifying epoxy resin emulsion is prepared by the following method: in the presence of a protective gas, the epoxy resin is first mixed with the sorbitan polyoxyethylene ether fatty acid ester The first reaction is carried out in the presence of an amine accelerator, and then the second reaction is carried out with the fatty alcohol polyether phosphate, and then mixed with the water.
  • the protective gas may be nitrogen, argon, or the like.
  • the reaction temperature of the first reaction is 180-190°C.
  • the reaction temperature of the second reaction is 70-90°C.
  • the epoxy resin is a combination of one or more selected from bisphenol A epoxy resins.
  • the epoxy resin is composed of at least one selected from the group consisting of bisphenol A epoxy resin E12 and bisphenol A epoxy resin E20, and at least one selected from bisphenol A epoxy resin E44 and At least one type of bisphenol A epoxy resin E51 is constituted.
  • the amine accelerator is at least one selected from the group consisting of diethanolamine, triethanolamine and N,N-dimethylbenzylamine.
  • the water is deionized water.
  • a preparation method of the self-emulsifying epoxy resin emulsion described above includes the following steps:
  • the protective gas may be nitrogen, argon, or the like.
  • step (3) the stirring is performed at 40-50°C.
  • a two-component epoxy coating includes A component and B component, and the mass ratio of the A component to the B component It is 1:0.95-1.05.
  • the A component includes:
  • the balance is water
  • the B component includes:
  • the wetting and dispersing agent is: dispersing agent SN-5040.
  • the defoamer is: Dow Corning DC-65.
  • the leveling agent is: German KANON CN-301.
  • the water-soluble epoxy curing agent is: Dow D.E.H.805.
  • the neutralizer is triethanolamine, diethanolamine and the like.
  • the water is deionized water.
  • the present invention has the following advantages compared with the prior art:
  • the present invention innovatively uses anhydrous sorbitan polyoxyethylene ether fatty acid ester and fatty alcohol polyether phosphate to modify the epoxy resin, which not only endows the modified epoxy resin without adding a co-solvent
  • the preparation method is as follows:
  • the preparation method is as follows:
  • This example provides a self-emulsifying epoxy resin emulsion, in parts by mass, its raw materials include 100 parts of bisphenol A epoxy resin E-44, 30 parts of bisphenol A epoxy resin E12, and 10 parts of Tween 60, 15 Parts of polyoxyethylene laureth (AE06) phosphate, 5 parts of diethanolamine and 400 parts of deionized water.
  • its raw materials include 100 parts of bisphenol A epoxy resin E-44, 30 parts of bisphenol A epoxy resin E12, and 10 parts of Tween 60, 15 Parts of polyoxyethylene laureth (AE06) phosphate, 5 parts of diethanolamine and 400 parts of deionized water.
  • the preparation method is as follows:
  • This example provides an epoxy resin emulsion, in parts by mass, its raw materials include 100 parts of bisphenol A epoxy resin E-51, 20 parts of bisphenol A epoxy resin E12, 5 parts of Tween 80, and 5 parts of two parts. 400 parts of ethanolamine and deionized water.
  • the preparation method is as follows:
  • reaction product is slowly added to deionized water under stirring conditions, and the temperature of the emulsion is controlled to about 45° C. After all the reaction products are added to the deionized water, the epoxy resin emulsion is prepared by stirring.
  • Example 2 It is basically the same as Example 2, except that the addition amount of Tween 80 is adjusted to 5 parts.
  • Examples 7 days 30 days 60 days 90 days 180 days Example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Example 2 Stable no stratification Stable no stratification Stable no stratification Stable No stratification Stable no stratification Example 3 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Comparative example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Slight Stratification Comparative Example 2 Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification
  • Examples 7 days 30 days 60 days 90 days 180 days Example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Example 2 Stable no stratification Stable no stratification Stable no stratification Stable No stratification Stable no stratification Example 3 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Comparative example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Slight Stratification Comparative Example 2 Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification
  • the experimental condition is a neutral salt spray test, using 5% sodium chloride aqueous solution
  • the application experiment of this example provides a two-component epoxy coating, the two-component epoxy coating includes A component and B component, and the mass ratio of the A component to the B component is 1:1 , See Table 5 below for specific formulation materials and dosages.
  • Preparation method (1) Preparation of component A: weigh each raw material according to the formula, and then mix to make; (2) Preparation of component B: weigh each raw material according to the formula, and then mix to make;

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明公开了一种自乳化环氧树脂乳液及其制备方法和应用,其原料包括环氧树脂100-150份、失水山梨醇聚氧乙烯醚脂肪酸酯10-20份、脂肪醇聚醚磷酸酯10-20份、胺类促进剂1-5份和水100-10000份;环氧树脂与失水山梨醇聚氧乙烯醚脂肪酸酯、脂肪醇聚醚磷酸酯的投料质量比分别为1∶0.075-0.18、1∶0.07-0.2;制备:使环氧树脂与失水山梨醇聚氧乙烯醚脂肪酸酯在胺类促进剂存在下进行第一反应,再与脂肪醇聚醚磷酸酯进行第二反应,然后与水混合制成;及其在环氧涂料中的应用;本发明能够在不加助溶剂的情况下自乳化成均匀稳定的乳液,储存周期长,无VOC排放,成膜后兼具优异的漆膜韧性和防锈性能。

Description

一种自乳化环氧树脂乳液及其制备方法和应用
本申请要求申请号为:CN201911212817.4、申请日为2019.12.2的中国国家知识产权局的在先专利申请为优先权,该在先专利申请文本中的内容通过引用而完全加入本专利申请中。
技术领域
本发明属于水性涂料技术领域,具体涉及一种自乳化环氧树脂乳液及其制备方法和应用。
背景技术
环氧树脂因其粘接性能好,机械强度高以及固化收缩率小的特性,被广泛应用于建筑、木器、五金、电子电器等各行各业。传统的环氧树脂涂料以有机溶剂作为稀释剂,对环境和涂料作业人员的身心健康造成直接损害。随着环保要求越来越高,传统的环氧树脂涂料已经不能满足,急需提出可持续发展的解决方案。
环氧乳液以水作溶剂,克服了传统环氧涂料因有机溶剂而带来的VOC问题,同时还完好地保持了原来涂料的各项性能,具有极佳的经济价值与应用价值。但是目前大部分的环氧乳液都存在一些问题:(1)储存稳定性差;(2)较高的固化膜硬度,柔韧性差漆膜易开裂;(3)需要添加助溶剂不能做到完全零VOC排放;(4)防腐性能差,易生锈,这些都限制了水性环氧乳液的使用。
发明内容
本发明的目的在于克服现有技术的不足,提供一种新型的自乳化环氧树脂乳液,其能够在不添加助溶剂的情况下而自乳化成均匀稳定的乳液,储存周期长,真正实现了零VOC排放;同时成膜后还能兼具优异的漆膜韧性以及防锈性能。
本发明同时还提供了一种上述自乳化环氧树脂乳液的制备方法。
本发明同时还提供了一种包含上述自乳化环氧树脂乳液的环氧涂料。
为解决上述技术问题,本发明采取如下技术方案:
一种自乳化环氧树脂乳液,其原料包括环氧树脂和水,所述原料还包括失水山梨醇聚氧乙烯醚脂肪酸酯、脂肪醇聚醚磷酸酯和胺类促进剂;以质量份数计,所述原料中,环氧树脂100-150份、失水山梨醇聚氧乙烯醚脂肪酸酯10-20份、脂肪醇聚醚磷酸酯10-20份、胺类促进剂1-5份和水100-10000份;其中,所述失水山梨醇聚氧乙烯醚脂肪酸酯与所述环氧树脂的投料质量比为0.075-0.180∶1,所述脂肪醇聚醚磷酸酯与所述环氧树脂的投料质量比为0.07-0.20∶1。
根据本发明的一些优选且具体的方面,所述失水山梨醇聚氧乙烯醚脂肪酸酯为选自吐温20、吐温60和吐温80中的一种或多种的组合。
根据本发明的一些优选且具体的方面,所述脂肪醇聚醚磷酸酯为选自月桂醇聚氧乙烯醚磷酸酯、异辛醇聚氧乙烯醚磷酸酯和异构十三醇聚氧乙烯醚磷酸酯中的一种或多种的组合。
根据本发明的一些具体且优选的方面,所述脂肪醇聚醚磷酸酯为选自月桂醇聚氧乙烯醚(AE03)磷酸酯、月桂醇聚氧乙烯醚(AE06)磷酸酯、月桂醇聚氧乙烯醚(AE09)磷酸酯、异辛醇聚氧乙烯醚(n=3)磷酸酯、异辛醇聚氧乙烯醚(n=6)磷酸酯、异构十三醇聚氧乙烯醚(n=3)磷酸酯和异构十三醇聚氧乙烯醚(n=6)磷酸酯中的一种或多种的组合。
根据本发明的一些优选方面,所述自乳化环氧树脂乳液通过如下方法制备而得:在保护气体存在下,使所述环氧树脂先与所述失水山梨醇聚氧乙烯醚脂肪酸酯在胺类促进剂存在下进行第一反应,再与所述脂肪醇聚醚磷酸酯进行第二反应,然后与所述水混合制成。
根据本发明的一些具体方面,所述保护气体可以为氮气、氩气等等。
根据本发明的一些优选方面,所述第一反应的反应温度为180-190℃。
根据本发明的一些优选方面,所述第二反应的反应温度为70-90℃。
根据本发明的一些具体方面,所述环氧树脂为选自双酚A型环氧树脂中的一种或多种的组合。
根据本发明的一些优选方面,所述环氧树脂由选自双酚A型环氧树脂E12和双酚A型环氧树脂E20中的至少一种与选自双酚A型环氧树脂E44和双酚A型环氧树脂E51中的至少一种构成。
根据本发明的一些具体且优选的方面,所述胺类促进剂为选自二乙醇胺、三乙醇胺和N,N-二甲基苄胺中的至少一种。
根据本发明的一些具体方面,所述水为去离子水。
本发明提供的又一技术方案:一种上述所述的自乳化环氧树脂乳液的制备方法,所述制备方法包括如下步骤:
(1)将环氧树脂和失水山梨醇聚氧乙烯醚脂肪酸酯加热至110-130℃,然后真空脱除水分,并通保护气体进行保护;
(2)将胺类促进剂加入经脱水处理的环氧树脂和失水山梨醇聚氧乙烯醚脂肪酸酯的混合溶液中,然后升温,控制温度在180~190℃之间反应;
(3)降温至70-90℃,加入脂肪醇聚醚磷酸酯反应,然后将反应产物在搅拌条件下加入水中,待反应产物全部加入到水中后,搅拌制得所述自乳化环氧树脂乳液。
根据本发明的一些具体方面,步骤(1)中,所述保护气体可以为氮气、氩气等等。
根据本发明的一些具体方面,步骤(3)中,所述搅拌在40-50℃下进行。
本发明提供的又一技术方案:一种双组份环氧涂料,所述双组份环氧涂料包括A组分和B组分,所述A组分与所述B组分的投料质量比为1∶0.95-1.05。
根据本发明的一些具体且优选的方面,以质量百分含量计,所述A组分包括:
权利要求1-8中任一项权利要求所述的自乳化环氧树脂乳液30-50%;
润湿分散剂0.1-1%;
消泡剂0.1-1%;
流平剂0.1-1%;
余量为水;
以质量百分含量计,所述B组分包括:
水溶性环氧固化剂90-99%;
中和剂1-10%。
根据本发明的一些具体方面,所述润湿分散剂为:分散剂SN-5040。
根据本发明的一些具体方面,所述消泡剂为:道康宁DC-65。
根据本发明的一些具体方面,所述流平剂为:德国KANON CN-301。
根据本发明的一些具体方面,所述水溶性环氧固化剂为:美国陶氏D.E.H.805。
根据本发明的一些具体方面,所述中和剂为三乙醇胺、二乙醇胺等。
根据本发明的一些具体方面,所述水为去离子水。
由于以上技术方案的实施,本发明与现有技术相比具有如下优点:
本发明创新地采用失水山梨醇聚氧乙烯醚脂肪酸酯和脂肪醇聚醚磷酸酯分别对环氧树脂进行改性,不仅赋予了改性后的环氧树脂在不添加助溶剂的情况下而自乳化成均匀稳定的乳液的能力,而且储存周期长,真正实现了零VOC排放;同时成膜后还能兼具优异的漆膜韧性以及防锈性能,进而使得水性环氧树脂能够得到广泛应用,充分发挥环氧树脂自身特性,符合环保的高标准要求。
具体实施方式
以下结合具体实施例对本发明做进一步详细说明。应理解,这些实施例用于说明本发明的基本原理、主要特征和优点,而本发明不受以下实施例的限制。实施例中采用的实施条件可以根据具体要求做进一步调整,未注明的实施条件通常为常规实验中的条件。实施例所用原料均为可商购的工业品。
下述实施例中,如无特殊说明,所有的原料基本来自于商购或者通过本领域的常规方法制备而得。下述中,双酚A环氧树脂E-44购自昆山南亚,双酚A环氧树脂E-51购自昆山南亚,双酚A环氧树脂E12购自昆山南亚,吐温20购自浙江皇马化工,吐温60购自浙江皇马化工,吐温80购自浙江皇马化工,月桂醇聚氧乙烯醚(n=3)磷酸酯购自浙江皇马化工,月桂醇聚氧乙烯醚(AE06)磷酸酯购自浙江皇马化工。
实施例1
本例提供一种自乳化环氧树脂乳液,以质量份数计,其原料包括100份双酚A环氧树脂E-44、30份双酚A环氧树脂E12、10份吐温20、10份月桂醇聚氧乙烯醚(n=3)磷酸酯、5份二乙醇胺和去离子水300份。
制备方法如下:
(1)将双酚A环氧树脂E-44、双酚A环氧树脂E12和吐温20加热至120℃左右,然后真空脱除水分,并通氮气进行保护;
(2)将二乙醇胺加入经脱水处理的双酚A环氧树脂E-44、双酚A环氧树脂E12和吐温20的混合溶液中,然后升温,控制温度在185℃左右反应;
(3)降温至80℃左右,加入月桂醇聚氧乙烯醚(n=3)磷酸酯反应,然后将反应产物在搅拌条件下缓慢加入去离子水中,控制乳液温度为45℃左右,待反应产物全部加入到去离子水中后,搅拌制得所述自乳化环氧树脂乳液。
实施例2
本例提供一种自乳化环氧树脂乳液,以质量份数计,其原料包括100份双酚A环氧树脂E-51、20份双酚A环氧树脂E12、10份吐温80、10份月桂醇聚氧乙烯醚(n=3)磷酸酯、5份二乙醇胺和去离子水400份。
制备方法如下:
(1)将双酚A环氧树脂E-51、双酚A环氧树脂E12和吐温80加热至120℃左右,然后真空脱除水分,并通氮气进行保护;
(2)将二乙醇胺加入经脱水处理的双酚A环氧树脂E-51、双酚A环氧树脂E12和吐温80的混合溶液中,然后升温,控制温度在185℃左右反应;
(3)降温至80℃左右,加入月桂醇聚氧乙烯醚(n=3)磷酸酯反应,然后将反应产物在搅拌条件下缓慢加入去离子水中,控制乳液温度为45℃左右,待反应产物全部加入到去离子水中后,搅拌制得所述自乳化环氧树脂乳液。
实施例3
本例提供一种自乳化环氧树脂乳液,以质量份数计,其原料包括100份双酚A环氧树脂E-44、30份双酚A环氧树脂E12、10份吐温60、15份月桂醇聚氧乙烯醚(AE06)磷酸酯、5份二乙醇胺和去离子水400份。
制备方法如下:
(1)将双酚A环氧树脂E-44、双酚A环氧树脂E12和吐温60加热至110-130℃,然后真空脱除水分,并通氮气进行保护;
(2)将二乙醇胺加入经脱水处理的双酚A环氧树脂E-44、双酚A环氧树脂E12和吐温60的混合溶液中,然后升温,控制温度在185℃左右反应;
(3)降温至80℃左右,加入月桂醇聚氧乙烯醚(AE06)磷酸酯反应,然后将反应产物在搅拌条件下缓慢加入去离子水中,控制乳液温度为45℃左右,待反应产物全部加入到去离子水中后,搅拌制得所述自乳化环氧树脂乳液。
对比例1
本例提供一种环氧树脂乳液,以质量份数计,其原料包括100份双酚A环氧树脂E-51、20份双酚A环氧树脂E12、5份吐温80、5份二乙醇胺和去离子水400份。
制备方法如下:
(1)将双酚A环氧树脂E-51、双酚A环氧树脂E12和吐温80加热至120℃左右,然后真空脱除水分,并通氮气进行保护;
(2)将二乙醇胺加入经脱水处理的双酚A环氧树脂E-51、双酚A环氧树脂E12和吐温80的混合溶液中,然后升温,控制温度在185℃左右反应;
(3)然后将反应产物在搅拌条件下缓慢加入去离子水中,控制乳液温度为45℃左右,待反应产物全部加入到去离子水中后,搅拌制得环氧树脂乳液。
对比例2
基本同实施例2,其区别仅在于:将吐温80的添加量调整为5份。
性能测试
将上述实施例1-3以及对比例1-2所获得的环氧树脂乳液分别进行如下一些性能测试。
(一)、乳液稳定性测试(采用静置方式,目测)
表1、常温测试
实例 7天 30天 60天 90天 180天 实施例1 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层 实施例2 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层 实施例3 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分 层 对比例1 稳定无分层 稳定无分层 稳定无分层 稳定无分层 轻微分层 对比例2 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层
表2、50℃高温测试
Figure PCTCN2020121847-appb-000001
实例 7天 30天 60天 90天 180天 实施例1 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层 实施例2 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层 实施例3 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层 对比例1 稳定无分层 稳定无分层 稳定无分层 稳定无分层 轻微分层 对比例2 稳定无分层 稳定无分层 稳定无分层 稳定无分层 稳定无分层
(二)、漆膜柔韧性测试(测试标准:GB/T 1731-93)
表3
Figure PCTCN2020121847-appb-000002
注:圆棒直径越小,没有裂纹说明柔韧性越好
(三)、乳液防锈性能测试(测试标准:GB6458-86)
表4
Figure PCTCN2020121847-appb-000003
注:实验条件为中性盐雾试验,使用5%氯化钠水溶液
应用实验
本例应用实验提供一种双组份环氧涂料,所述双组份环氧涂料包括A组分和B组分,所述A组分与所述B组分的投料质量比为1∶1,具体配方原料以及用量参见下表5。
表5
Figure PCTCN2020121847-appb-000004
制备方法:(1)A组分的制备:按配方量称取各原料,然后混合即制成;(2)B组分的制备:按配方量称取各原料,然后混合即制成;
应用时按配方量称取A、B组分,混合后即可涂覆喷涂。
双组份环氧涂料性能测试:
表6
Figure PCTCN2020121847-appb-000005
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种自乳化环氧树脂乳液,其原料包括环氧树脂和水,其特征在于,所述原料还包括失水山梨醇聚氧乙烯醚脂肪酸酯、脂肪醇聚醚磷酸酯和胺类促进剂;以质量份数计,所述原料中,环氧树脂100-150份、失水山梨醇聚氧乙烯醚脂肪酸酯10-20份、脂肪醇聚醚磷酸酯10-20份、胺类促进剂1-5份和水100-10000份;其中,所述失水山梨醇聚氧乙烯醚脂肪酸酯与所述环氧树脂的投料质量比为0.075-0.180∶1,所述脂肪醇聚醚磷酸酯与所述环氧树脂的投料质量比为0.07-0.20∶1。
  2. 根据权利要求1所述的自乳化环氧树脂乳液,其特征在于,所述失水山梨醇聚氧乙烯醚脂肪酸酯为选自吐温20、吐温60和吐温80中的一种或多种的组合。
  3. 根据权利要求1所述的自乳化环氧树脂乳液,其特征在于,所述脂肪醇聚醚磷酸酯为选自月桂醇聚氧乙烯醚磷酸酯、异辛醇聚氧乙烯醚磷酸酯和异构十三醇聚氧乙烯醚磷酸酯中的一种或多种的组合。
  4. 根据权利要求1-3中任一项权利要求所述的自乳化环氧树脂乳液,其特征在于,所述自乳化环氧树脂乳液通过如下方法制备而得:在保护气体存在下,使所述环氧树脂先与所述失水山梨醇聚氧乙烯醚脂肪酸酯在胺类促进剂存在下进行第一反应,再与所述脂肪醇聚醚磷酸酯进行第二反应,然后与所述水混合制成。
  5. 根据权利要求4所述的自乳化环氧树脂乳液,其特征在于,所述第一反应的反应温度为180-190℃;和/或,所述第二反应的反应温度为70-90℃。
  6. 根据权利要求1所述的自乳化环氧树脂乳液,其特征在于,所述环氧树脂为选自双酚A型环氧树脂中的一种或多种的组合。
  7. 根据权利要求6所述的自乳化环氧树脂乳液,其特征在于,所述环氧树脂由选自双酚A型环氧树脂E12和双酚A型环氧树脂E20中的至少一种与选自双酚A型环氧树脂E44和双酚A型环氧树脂E51中的至少一种构成。
  8. 根据权利要求1所述的自乳化环氧树脂乳液,其特征在于,所述胺类促进剂为选自二乙醇胺、三乙醇胺和N,N-二甲基苄胺中的至少一种。
  9. 一种权利要求1-8中任一项权利要求所述的自乳化环氧树脂乳液的制备方法,其特征在于,所述制备方法包括如下步骤:
    (1)将环氧树脂和失水山梨醇聚氧乙烯醚脂肪酸酯加热至110-130℃,然后真空脱除水分,并通保护气体进行保护;
    (2)将胺类促进剂加入经脱水处理的环氧树脂和失水山梨醇聚氧乙烯醚脂肪酸酯的混合溶液中,然后升温,控制温度在180~190℃之间反应;
    (3)降温至70-90℃,加入脂肪醇聚醚磷酸酯反应,然后将反应产物在搅拌条件下加入水中,待反应产物全部加入到水中后,搅拌制得所述自乳化环氧树脂乳液。
  10. 一种双组份环氧涂料,所述双组份环氧涂料包括A组分和B组分,其特征在于,所述A组分与所述B组分的投料质量比为1∶0.95-1.05;
    其中,以质量百分含量计,所述A组分包括:
    权利要求1-8中任一项权利要求所述的自乳化环氧树脂乳液30-50%;
    润湿分散剂0.1-1%;
    消泡剂0.1-1%;
    流平剂0.1-1%;
    余量为水;
    以质量百分含量计,所述B组分包括:
    水溶性环氧固化剂90-99%;
    中和剂1-10%。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116376032A (zh) * 2022-12-30 2023-07-04 鲁东大学 一种用于水性环氧防腐涂料树脂的生物质基乳化剂及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110804371B (zh) * 2019-12-02 2021-11-19 苏州太湖电工新材料股份有限公司 一种自乳化环氧树脂乳液及其制备方法和应用
CN112574643B (zh) * 2020-12-16 2022-02-11 苏州太湖电工新材料股份有限公司 一种阻燃型水性绝缘漆及其制备方法和应用
CN114213593A (zh) * 2021-12-21 2022-03-22 衡水新光新材料科技有限公司 一种氯丙金属防护漆用乳液及其制备方法及应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020111422A1 (en) * 2000-12-08 2002-08-15 Back Gayle Edward Water dispersible epoxy resins
JP2003327661A (ja) * 2002-05-07 2003-11-19 Asahi Denka Kogyo Kk 水性エポキシ樹脂用変性剤
CN106947359A (zh) * 2017-03-31 2017-07-14 哈尔滨工业大学(威海) 一种水性环氧树脂胶体及其制备方法
CN109384941A (zh) * 2018-09-19 2019-02-26 惠州市惠阳区嘉泰涂料有限公司 一种环氧树脂水基乳液的相反转乳化制备方法
CN110804371A (zh) * 2019-12-02 2020-02-18 苏州太湖电工新材料股份有限公司 一种自乳化环氧树脂乳液及其制备方法和应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117390B (zh) * 2007-09-18 2010-12-22 天津大学 水性环氧乳液的制备方法
KR100938127B1 (ko) * 2009-11-12 2010-01-22 (주)휴먼텍코리아엔지니어링건축사사무소 수성 에폭시 도료 조성물
CN104152009B (zh) * 2014-08-26 2016-08-24 南京林业大学 环氧丙烯酸酯防锈乳液的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020111422A1 (en) * 2000-12-08 2002-08-15 Back Gayle Edward Water dispersible epoxy resins
JP2003327661A (ja) * 2002-05-07 2003-11-19 Asahi Denka Kogyo Kk 水性エポキシ樹脂用変性剤
CN106947359A (zh) * 2017-03-31 2017-07-14 哈尔滨工业大学(威海) 一种水性环氧树脂胶体及其制备方法
CN109384941A (zh) * 2018-09-19 2019-02-26 惠州市惠阳区嘉泰涂料有限公司 一种环氧树脂水基乳液的相反转乳化制备方法
CN110804371A (zh) * 2019-12-02 2020-02-18 苏州太湖电工新材料股份有限公司 一种自乳化环氧树脂乳液及其制备方法和应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116376032A (zh) * 2022-12-30 2023-07-04 鲁东大学 一种用于水性环氧防腐涂料树脂的生物质基乳化剂及其制备方法

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