CN107189055A - 水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体 - Google Patents

水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体 Download PDF

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CN107189055A
CN107189055A CN201710533540.XA CN201710533540A CN107189055A CN 107189055 A CN107189055 A CN 107189055A CN 201710533540 A CN201710533540 A CN 201710533540A CN 107189055 A CN107189055 A CN 107189055A
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monoisocyanates
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刘晓非
杜则冰
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Anhui Chemical Technology Co Ltd Apple Sid
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Abstract

本发明公开了一种水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体，涉及水性树脂合成技术领域，由如下质量百分比的原料制成：2,4‑甲苯二异氰酸酯11‑44％、聚乙二醇单甲醚56‑89％。本发明制得结构规整、水溶性和水乳性好的单异氰酸酯聚氧乙烯单甲醚亲水单体，NCO当量为500‑1700克/摩尔，该亲水单体结构中所含的异氰酸酯基团能与环氧树脂结构中的仲羟基反应而制得水性环氧树脂乳液。

Description

水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体
技术领域：
本发明涉及水性树脂合成技术领域，具体涉及一种水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体。
背景技术：
环氧树脂具有粘结性好、固化收缩率低、机械强度高、耐腐蚀性及耐溶剂性良好等优点，在化工、电器、建筑、航空等领域有着广泛的应用。传统的环氧树脂多为溶剂型环氧树脂，溶剂的使用会产生大量的挥发性有机化合物，污染环境且对人体健康造成不利影响。水性环氧树脂作为一种环境友好型产品，越来越受到人们关注。但是环氧树脂本身不溶于水，不能直接加水进行乳化，必须在其分子链中引入亲水基团或在体系中加入亲水亲油组分。
目前，环氧树脂水性化主要包括以下三种方法：机械法、化学改性法和相反转法。其中化学该刑法制备的水性环氧树脂乳液中分散相粒子的尺寸很小，约为几十到几百个纳米，但化学改性法的制备步骤不易控制，产品制备成本高。为了解决这一问题，本公司开发出一种单异氰酸酯聚氧乙烯单甲醚亲水单体，其结构中所含的异氰酸酯基团能与环氧树脂结构上的仲羟基反应，形成氨基甲酸酯官能团，从而制得水性环氧树脂乳液，所得乳液的稳定性好，并且由其形成的涂膜耐水性和耐盐雾性强。
发明内容：
本发明所要解决的技术问题在于提供一种通过化学改性法改善环氧树脂水乳性的水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体。
本发明所要解决的技术问题采用以下的技术方案来实现：
水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体，由如下质量百分比的原料制成：
2,4-甲苯二异氰酸酯 11-44％
聚乙二醇单甲醚 56-89％。
所述聚乙二醇单甲醚的分子量在400-1500。
其制备方法为：将2,4-甲苯二异氰酸酯和聚乙二醇单甲醚混合后升温至40-100℃反应3-10h，自然冷却至室温，即得单异氰酸酯聚氧乙烯单甲醚亲水单体。
本发明的反应机理：
2,4-甲苯二异氰酸酯结构中的一个异氰酸酯基团与聚乙二醇单甲醚结构中的羟基反应生成单异氰酸酯聚氧乙烯单甲醚亲水单体，所制单异氰酸酯聚氧乙烯单甲醚亲水单体的结构包含一个异氰酸酯基团，该异氰酸酯基团能与环氧树脂结构中的仲羟基反应，从而制得水性环氧树脂乳液。
本发明的有益效果是：
(1)本发明制得结构规整、水溶性和水乳性好的单异氰酸酯聚氧乙烯单甲醚亲水单体，NCO当量为500-1700克/摩尔，该亲水单体结构中所含的异氰酸酯基团能与环氧树脂结构中的仲羟基反应而制得水性环氧树脂乳液；
(2)本发明所制单异氰酸酯聚氧乙烯单甲醚亲水单体能替代乳化剂制得乳化效果好且质量稳定性好的水性环氧树脂乳液，并能提高所形成涂膜的耐水性和耐盐雾性；
(3)本发明单异氰酸酯聚氧乙烯单甲醚亲水单体的反应条件温和，且反应结束后无需后处理操作，显著降低水性环氧树脂乳液的制备成本。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例1
单异氰酸酯聚氧乙烯单甲醚亲水单体由如下质量百分比的原料制成：
2,4-甲苯二异氰酸酯 20％
聚乙二醇单甲醚 80％
将2,4-甲苯二异氰酸酯和聚乙二醇单甲醚混合后升温至100℃反应5h，自然冷却至室温，即得单异氰酸酯聚氧乙烯单甲醚亲水单体。
实施例2
单异氰酸酯聚氧乙烯单甲醚亲水单体由如下质量百分比的原料制成：
2,4-甲苯二异氰酸酯 25％
聚乙二醇单甲醚 75％
将2,4-甲苯二异氰酸酯和聚乙二醇单甲醚混合后升温至60℃反应8h，自然冷却至室温，即得单异氰酸酯聚氧乙烯单甲醚亲水单体。
实施例3
单异氰酸酯聚氧乙烯单甲醚亲水单体由如下质量百分比的原料制成：
2,4-甲苯二异氰酸酯 15％
聚乙二醇单甲醚 85％
将2,4-甲苯二异氰酸酯和聚乙二醇单甲醚混合后升温至80℃反应6h，自然冷却至室温，即得单异氰酸酯聚氧乙烯单甲醚亲水单体。
实施例4
分别将实施例1、实施例2、实施例3所制单异氰酸酯聚氧乙烯单甲醚亲水单体按照如下质量百分比制备水性环氧乳液；
将环氧树脂E20、亚油酸和二甲苯溶剂的混合物升温至200℃酯化到酸值为5-6，降温至120℃，真空脱水使树脂中的二甲苯和水含量降低至0.1％以下，继续降温至70℃，再加入单异氰酸酯聚氧乙烯单甲醚，保温反应5h，反应结束后滴加去离子水，直至相反转得到稳定的乳液。
对照例1
水性环氧乳液由如下质量百分比的原料制成：
将环氧树脂E20、亚油酸在200℃酯化至酸值为5-6，降温至150℃，再加入偏苯三酸酐酯化至酸值为50-60，继续降温到100℃真空脱水，并加入二甲苯降温至60℃，经三乙胺中和后加去离子水得到水性环氧乳液。
实施例5
将实施例4中分别利用实施例1、实施例2、实施例3所制水性环氧树脂乳液在4000r/min转速下离心30min，观察乳液是否分层；并将实施例4中分别利用实施例1、实施例2、实施例3所制水性环氧树脂乳液制备清漆涂膜，养护一周后依照国标GB/T22374-2008、GB/T1771-2007测试涂膜的耐水性和耐盐雾性，结果如表1所示，以对照例1所制水性环氧乳液作为对照。
表1乳液稳定性和涂膜耐水性、耐盐雾性试验结果
组别 清液高度 酸值 VOC含量 耐水时间/h 耐盐雾时间/h
实施例1 ＜1mm 5-6 10-15 240 144
实施例2 ＜1mm 4-5 10-15 260 168
实施例3 ＜1mm 4-5 10-15 240 156
对照例1 ＞2mm 50-60 20-25 164 96
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (3)

1.水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体，其特征在于，由如下质量百分比的原料制成：
2,4-甲苯二异氰酸酯 11-44％
聚乙二醇单甲醚 56-89％。
2.根据权利要求1所述的水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体，其特征在于：所述聚乙二醇单甲醚的分子量在400-1500。
3.根据权利要求1所述的水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体，其特征在于，其制备方法为：将2,4-甲苯二异氰酸酯和聚乙二醇单甲醚混合后升温至40-100℃反应3-10h，自然冷却至室温，即得单异氰酸酯聚氧乙烯单甲醚亲水单体。
CN201710533540.XA 2017-07-03 2017-07-03 水性环氧树脂合成用单异氰酸酯聚氧乙烯单甲醚亲水单体 Withdrawn CN107189055A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021088410A1 (zh) * 2019-11-06 2021-05-14 江苏中路工程技术研究院有限公司 热拌环氧沥青用超高韧环氧树脂材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619128A (zh) * 2009-07-31 2010-01-06 中国科学院广州化学研究所 酰胺封端非离子型水性异氰酸酯及其制备方法与应用
CN102977376A (zh) * 2012-11-29 2013-03-20 西安交通大学 非离子型自乳化水性环氧树脂及其制备方法及应用
CN104945633A (zh) * 2015-06-02 2015-09-30 江苏奥莱特新材料有限公司 一种新型聚羧酸系减水剂的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619128A (zh) * 2009-07-31 2010-01-06 中国科学院广州化学研究所 酰胺封端非离子型水性异氰酸酯及其制备方法与应用
CN102977376A (zh) * 2012-11-29 2013-03-20 西安交通大学 非离子型自乳化水性环氧树脂及其制备方法及应用
CN104945633A (zh) * 2015-06-02 2015-09-30 江苏奥莱特新材料有限公司 一种新型聚羧酸系减水剂的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021088410A1 (zh) * 2019-11-06 2021-05-14 江苏中路工程技术研究院有限公司 热拌环氧沥青用超高韧环氧树脂材料及其制备方法

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Application publication date: 20170922