CN109337567A - 一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料 - Google Patents

一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料 Download PDF

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CN109337567A
CN109337567A CN201811132911.4A CN201811132911A CN109337567A CN 109337567 A CN109337567 A CN 109337567A CN 201811132911 A CN201811132911 A CN 201811132911A CN 109337567 A CN109337567 A CN 109337567A
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谢义鹏
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Abstract

本发明涉及一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，由聚醚醚酮改性聚氨酯水性树脂、助溶剂、防锈及颜填料、纳米功能材料、助剂和去离子水组成；本发明制得的一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，具有优异的附着力、耐腐蚀性、耐磨性、耐盐雾性、耐老化性、耐水性、耐水蒸气性、抗闪锈性、自阻燃性和机械特性；广泛用于建筑物、化工、石油、电力、冶金、船舶、交通、航天等钢结构及混凝土的防腐涂料、耐磨涂料、防火阻燃涂料及地坪涂料。

Description

一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料
技术领域
本发明涉及一种改性聚氨酯树脂水性涂料，尤其涉及到一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，属于水性功能涂料技术领域。
背景技术
涂料是日常生产保护基础设施不可或缺的材料，被广泛应用于建筑物、各类五金件、工业制品的装饰以及机械、车辆、船舶、飞机、仪表等领域。丙烯酸树脂涂料具有原料价格便宜、对颜料润湿性好等优点，且具有良好的施工性，在涂料领域中一直扮演着重要角色。但传统的丙烯酸树脂涂料中含有大量有机溶剂，对人体和生态环境造成严重影响。
随着人们环境保护意识的增强，环境友好型水性涂料的生产及应用已是大势所趋。与溶剂型涂料相比，水性涂料中没有或很少含有可挥发性有机物(VOC)。其具有安全环保、成本低、施工灵活等多重优点。水性丙烯酸树脂涂料，以水为溶剂，其被广泛应用于各个领域。
目前水性防腐涂料防腐期限短，涂装后易闪锈，耐酸耐候性差，硬度和稳定性差等问题。而且聚氨酯涂料不适宜用于防火阻燃涂料，但聚氨酯的涂料性能具有优势，如耐腐蚀性、耐老化性和机械特性等，开发一种既具有优异的防腐性能，又能满足阻燃性能的多功能水性聚氨酯涂料将获得市场的青睐。
发明内容
聚醚醚酮是在主链结构中含有一个酮键和两个醚键的重复单元结构的聚合物，属于特种高分子材料，具有耐高温湿热性、耐水蒸汽性、耐腐蚀性、耐老化性、抗辐射性和自阻燃性能，是一类半结晶状高分子材料，其拉伸强度为132～148MPa，可用作耐高温阻燃材料、耐腐蚀材料、耐磨材料、抗辐射材料和电绝缘材料。
本发明采用PEEK改性水性聚氨酯树脂，在聚氨酯树脂分子骨架中含有一个酮键和两个醚键的重复单元，PEEK结构具有抗α、β、γ、X射线作用，其拉伸强度为132～148MPa，因此，PEEK改性的水性聚氨酯树脂能有效地提高涂膜的附着力、抗辐射性、耐腐蚀性、耐磨性、耐高温性、耐水蒸汽性、耐老化性、耐湿热性、电绝缘性、自阻燃性和机械特性。
本发明提供一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料。
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，按重量百分比计，其组分为：聚醚醚酮改性聚氨酯水性树脂30.0～65.0％、助溶剂2.0～8.0％、防锈颜料10.0～35.0％、颜填料10.0～25.0％、纳米功能材料1.0～12.0％、助剂1.0～10.0％、去离子水至100％。
所述聚醚醚酮改性聚氨酯水性树脂，基于申请的发明专利“一种聚醚醚酮改性聚氨酯水性树脂及制备方法”中所述，按重量份数计，其成分为：10.0～20.0份胺改性聚醚醚酮、20.0～30.0份低聚物多元醇、10.0～30.0份二异氰酸酯、3.0～6.0份亲水改性剂、稀释剂10.0～20.0份、0.03～0.3份催化剂、2.0～8.0份小分子醇扩链剂、2.0～5.0份三乙胺、0.8～2.0份有机胺扩链剂、120.0～180.0份去离子水。
所述聚醚醚酮改性聚氨酯水性树脂，其制备步骤如下：
a)在N2保护和搅拌条件下，向反应装置中依次加入二异氰酸酯、胺改性聚醚醚酮、低聚物多元醇、亲水改性剂，控制温度70～100℃下反应1～3h，取样检测，当所测得的-NCO值达到所规定的理论值时，降温至60～80℃停止反应；
b)加入稀释剂调节体系粘度，在转速为500～600rpm搅拌下加入小分子醇扩链剂和催化剂进行扩链反应，1h后开始取样当所测得的-NCO值达到所规定的理论值时，降温至室温停止反应，得到改性聚氨酯预聚物；
c)在保持搅拌转速和常温下，加入三乙胺，反应10～20min；接着加入80～90％的去离子水，之后提高转速到1000～1500rpm乳化10～30min，降低搅拌转速为500～600rpm；在10～30min内滴加完有机胺扩链剂溶液(预先将有机胺扩链剂溶解到10～20％的去离子水中)，在水相中进行扩链反应1～2h；然后减压蒸馏出溶剂，得所述聚醚醚酮改性聚氨酯水性树脂。
所述低聚物多元醇为聚酯多元醇或聚醚多元醇；所述聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇中的至少一种，其数均分子量Mn为1000～3000；所述聚醚多元醇为聚四氢呋喃醚二醇、聚四亚甲基醚二醇、聚环氧丙烷醚二醇中的至少一种，其数均分子量Mn为1000～3000。
所述二异氰酸酯为HDI、MDI、IPDI、HMDI中的至少一种。
所述亲水改性剂为2-羟基丙酸、2-吡咯烷酮、3-羟基丙酸、2-羟基丁酸中的至少一种。
所述稀释剂为丙酮、丁酮、N-甲基吡咯烷酮中的至少一种。
所述催化剂为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡中的至少一种。
所述小分子醇扩链剂为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、三羟甲基丙烷、新戊二醇、二甘醇的至少一种。
所述有机胺扩链剂为乙二胺、二乙烯三胺、己二胺、哌嗪中的至少一种。
所述助溶剂为醇类溶剂、醇酯类、醇醚类溶剂中的至少一种。
所述防锈颜料为磷酸锌、二硝基苯甲酸锌、硼酸锌、磷酸铝锌、氧化铁红、硅铬酸锌、三聚磷酸铝、钛铁粉、磷铁粉、铬酸锶、铬酸钡、石墨粉、偏硼酸钡、云母粉中的一种或几种的组合。
所述颜填料为滑石粉、高岭土、硅石粉、膨润土、硫酸钡、碳酸钙、钛白粉、氧化锌、水性色浆中的一种或几种的组合。
所述纳米功能材料为纳米SiO2、纳米Al2O3、纳米ZnO、纳米TiO2、纳米Fe2O3、纳米聚合物微球、纳米氮化硼、纳米氧化锆、碳纳米管、石墨烯中的至少一种。
所述助剂至少包括分散剂、基材润湿剂、消泡剂、流平剂、防沉流变剂、偶联剂、成膜助剂、防闪锈剂、pH调节剂中的至少两种以上。
本发明制得的一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，具有优异的附着力、耐腐蚀性、耐磨性、耐盐雾性、耐老化性、耐水性、耐水蒸气性、抗闪锈性、自阻燃性和机械特性；广泛用于建筑物、化工、石油、电力、冶金、船舶、交通、航天等钢结构及混凝土的防腐涂料、耐磨涂料、防火阻燃涂料及地坪涂料。
具体实施方式
本发明结合以下实施例对聚醚醚酮改性聚氨酯水性防腐耐磨涂料做进一步描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，按重量份计，其组成为：聚醚醚酮改性聚氨酯水性树脂A 42.0份、丙二醇甲醚2.5份、分散剂1.5份、磷酸锌12.0份、二硝基苯甲酸锌2.0份、偏硼酸钡6.0份、纳米SiO2 3.0份、云母粉6.0份、滑石粉10.0份、防闪锈剂0.5份、pH调节剂0.2份、有机膨润土1.5份、流平剂0.1份、消泡剂0.2份、去离子水12.5份
其中，所述聚醚醚酮改性聚氨酯水性树脂A为发明专利“一种聚醚醚酮改性聚氨酯水性树脂及制备方法”中的实施例4所述。
实施例2
一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，按重量份计，其组成为：聚醚醚酮改性聚氨酯水性树脂B 40.0份、丙二醇甲醚2.0份、分散剂1.5份、磷酸锌10.0份、硫酸钡5.0份、PMMA微球4.0份、纳米Al2O3 2.0份、硅烷偶联剂1.0份、云母粉10.0份、钛白粉6.0份、滑石粉6.0份、流平剂0.1份、消泡剂0.1份、有机膨润土2.0份、pH调节剂0.1份、去离子水10.2份；
其中，所述聚醚醚酮改性聚氨酯水性树脂B为发明专利“一种聚醚醚酮改性聚氨酯水性树脂及制备方法”中的实施例5所述。
实施例3
一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，按重量份计，其组成为：聚醚醚酮改性聚氨酯水性树脂C 40.0份、丙二醇单丁醚3.0份、硫酸钡6.0份、滑石粉12.0份、磷酸锌12.0份、石墨烯1.0份、钛白粉6.0份、偏硼酸钡4.0份、流平剂0.3份、分散剂1.5份、润湿剂0.2份、消泡剂0.2份、防沉剂0.5份、pH调节剂0.1份、去离子水13.2份；
其中，所述聚醚醚酮改性聚氨酯水性树脂C为发明专利“一种聚醚醚酮改性聚氨酯水性树脂及制备方法”中的实施例6所述。
实施例4
一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，按重量份计，其组成为：聚醚醚酮改性聚氨酯水性树脂A 55.0份、丙二醇丁醚3.0份、分散剂0.5份、磷酸锌10.0份、纳米氧化锆3.0份、钛白粉6.0份、pH调节剂0.1份、50％酞菁蓝色浆8.0份、消泡剂0.2份、防沉剂0.5份、流平剂0.2份、去离子水13.5份；
其中，所述聚醚醚酮改性聚氨酯水性树脂A为发明专利“一种聚醚醚酮改性聚氨酯水性树脂及制备方法”中的实施例4所述。
对本发明的实施例中的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，按照相关标准进行检测，其性能指标如表1所示。
表1：聚醚醚酮改性聚氨酯水性防腐耐磨涂料性能技术指标
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。

Claims (7)

1.一种聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其组成为：聚醚醚酮改性聚氨酯水性树脂30.0～65.0％、助溶剂2.0～8.0％、防锈颜料10.0～35.0％、颜填料10.0～25.0％、纳米功能材料1.0～12.0％、助剂1.0～10.0％、去离子水至100％；
其中，所述防锈颜料为磷酸锌、二硝基苯甲酸锌、硼酸锌、磷酸铝锌、氧化铁红、硅铬酸锌、三聚磷酸铝、钛铁粉、磷铁粉、铬酸锶、铬酸钡、石墨粉、偏硼酸钡、云母粉中的一种或几种的组合；所述纳米功能材料为纳米SiO2、纳米Al2O3、纳米ZnO、纳米TiO2、纳米Fe2O3、纳米聚合物微球、纳米氮化硼、纳米氧化锆、碳纳米管、石墨烯中的至少一种；
所述聚醚醚酮改性聚氨酯水性树脂，按重量份数计，其成分为：10.0～20.0份胺改性聚醚醚酮、20.0～30.0份低聚物多元醇、10.0～30.0份二异氰酸酯、3.0～6.0份亲水改性剂、10.0～20.0份稀释剂、0.03～0.3份催化剂、2.0～8.0份小分子醇扩链剂、2.0～5.0份三乙胺、0.8～2.0份有机胺扩链剂、120.0～180.0份去离子水；其制备步骤如下：
a)在N2保护和搅拌条件下，向反应装置中依次加入二异氰酸酯、胺改性聚醚醚酮、低聚物多元醇、亲水改性剂，控制温度70～100℃下反应1～3h，取样检测，当所测得的-NCO值达到所规定的理论值时，降温至60～80℃停止反应；
b)加入稀释剂调节体系粘度，在转速为500～600rpm搅拌下加入小分子醇扩链剂和催化剂进行扩链反应，1h后开始取样当所测得的-NCO值达到所规定的理论值时，降温至室温停止反应，得到改性聚氨酯预聚物；
c)预先将有机胺扩链剂溶解到10～20％的去离子水中待用；在保持搅拌转速和常温下，加入三乙胺，反应10～20min；接着加入80～90％的去离子水，之后提高转速到1000～1500rpm乳化10～30min，降低搅拌转速为500～600rpm；在10～30min内滴加完有机胺扩链剂溶液，在水相中进行扩链反应1～2h；然后减压蒸馏出溶剂，得所述聚醚醚酮改性聚氨酯水性树脂。
2.根据权利要求1所述的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述助溶剂为醇类溶剂、醇酯类、醇醚类溶剂中的至少一种。
3.根据权利要求1所述的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述助剂至少包括分散剂、基材润湿剂、消泡剂、流平剂、防沉流变剂、偶联剂、防闪锈剂、pH调节剂中的至少两种以上。
4.根据权利要求1所述的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述二异氰酸酯为HDI、MDI、IPDI、HMDI中的至少一种。
5.根据权利要求1所述的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述低聚物多元醇为聚酯多元醇或聚醚多元醇；所述聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇中的至少一种，其数均分子量Mn为1000～3000；所述聚醚多元醇为聚四氢呋喃醚二醇、聚四亚甲基醚二醇、聚环氧丙烷醚二醇中的至少一种，其数均分子量Mn为1000～3000。
6.根据权利要求1所述的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述稀释剂为丙酮、丁酮或N-甲基吡咯烷酮中的至少一种；所述催化剂为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡中的至少一种。
7.根据权利要求1所述的聚醚醚酮改性聚氨酯水性防腐耐磨涂料，其特征在于，所述小分子醇扩链剂为乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、三羟甲基丙烷、新戊二醇、二甘醇的至少一种；所述有机胺扩链剂为乙二胺、二乙烯三胺、己二胺、哌嗪中的至少一种。
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