CN109293874A - 一种聚醚醚酮改性聚氨酯水性树脂及制备方法 - Google Patents

一种聚醚醚酮改性聚氨酯水性树脂及制备方法 Download PDF

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CN109293874A
CN109293874A CN201811132907.8A CN201811132907A CN109293874A CN 109293874 A CN109293874 A CN 109293874A CN 201811132907 A CN201811132907 A CN 201811132907A CN 109293874 A CN109293874 A CN 109293874A
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谢义鹏
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Abstract

本发明涉及一种聚醚醚酮改性聚氨酯水性树脂,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;所述的聚醚醚酮改性聚氨酯水性树脂,其涂层具有优异的附着力、耐热水性、耐高温性、耐老化性、抗沾污性、电绝缘性、耐腐蚀性、抗辐射性、自阻燃性和机械性能,可以与其它水性树脂共混,用于水性防腐涂料、水性工程涂料、水性抗静电绝缘涂料和抗辐射涂料。

Description

一种聚醚醚酮改性聚氨酯水性树脂及制备方法
技术领域
本发明涉及一种改性聚氨酯水性树脂,尤其涉及到一种聚醚醚酮改性聚氨酯水性树脂,属于水性树脂技术领域。
技术背景
国内外相继制定了严厉的环保法规来限制挥发性有机化合物(VOC)向大气排放,高性能、环保化已成为涂料发展的方向。聚氨酯树脂的合成由传统的溶剂型向水性聚氨酯转变,水性聚氨酯涂料以水为溶剂,具有无污染、安全可靠、机械性能优良、相容性好、易于改性等优点,以其耐久性和耐化学性而著名,在木器漆领域与汽车涂料领域由于其优异的性能,受到用户的青睐。
但聚氨酯乳液存在固含量较小、成膜时间长、涂层可燃点低等缺点,专利和文章中存在大量有关改性水性聚氨酯研究与应用的发表。
中国专利CN105461863A公开了一种丙烯酸酯改性水性聚氨酯乳液及其制备方法,利用丙烯酸酯对水性聚氨酯进行改性,得到综合性能优异的聚氨酯材料,利用丙烯酸酯参与反应将双键引入到聚氨酯主链,随后引发丙烯酸单体的聚合,能够形成复杂的网状结构,相比较传统水性聚氨酯来说,耐水性、耐热性、力学性能有了明显的提高。
例如,中国专利CN106752830A公开了一种用于电力金具防腐的高强度复合有机硅改性聚氨酯水性涂料及其制备方法,该涂料以磺化聚醚醚酮乳液、有机硅改性聚氨酯乳液、水溶性聚丁二烯树脂复合作为成膜材料,不含有机溶剂,其具有良好的附着力,膜层固化速度快,抗化学腐蚀能力强,此外,原料中加入的经聚多巴胺膜包覆处理的腐植酸钠修饰的多壁碳纳米管和纳米陶瓷粉复合填料在树脂乳液中具有良好的分散性,显著的提高涂层的强度和抗腐耐磨性,再结合其它原料,该发明最终获得了一种新型环保高效的复合水性涂料,其对电力金具具有长效的防腐保护效果,延长了金具的使用寿命。但是该发明仅将磺化聚醚醚酮乳液与聚氨酯乳液作物理混合,涂料涂膜长时间后存在二者容易发生相分离、涂料强度降低等缺点。
发明内容
本发明旨在提供一种聚醚醚酮改性聚氨酯水性树脂及其制备方法。
所述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,具有耐高温阻燃性、耐热水性、耐化学品腐蚀性、抗辐射性等性能,是一类半结晶状高分子材料,其拉伸强度为132~148MPa,可用作耐高温阻燃结构材料、电绝缘材料。
本发明所述的聚醚醚酮改性聚氨酯水性树脂,通过改性的聚醚醚酮与异氰酸酯反应在聚氨酯分子结构上引入聚醚醚酮单元,在聚氨酯分子骨架上含有一个酮键和两个醚键的重复单元,能有效提高水性聚氨酯树脂成膜后的硬度、拉伸强度和柔韧性,涂层具有耐高温性、耐热水性、耐老化性、耐磨性、电绝缘性、阻燃性和耐腐蚀性。
为克服现有技术的缺点和不足,本发明采取以下技术方案,所述的一种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。
其中,所述胺改性聚醚醚酮,其制备步骤如下:
a)将10.0~20.0份浓硫酸加入到反应器中,在0℃下缓慢加入10.0~15.0份聚醚醚酮粉末和2.0~5.0份缩合剂,搅拌溶液至澄清,然后迅速加入5.0~10.0份甲基化试剂,继续在0℃下反应2~4h后停止搅拌,将反应物倒入冰水中得到白色絮状产物,为氯甲基化聚醚醚酮,抽滤,并用蒸馏水将产物反复洗至中性,再用乙醇洗涤3~5遍后干燥,得氯甲基化的聚醚醚酮;
b)将2.0~3.0份氯甲基化的聚醚醚酮溶解于10.0~15.0份有机溶剂中,搅拌溶解均匀,随后滴加0.1~0.4份的小分子有机胺,在0.5~1h内滴加完毕,在常温下反应4~8h,然后用旋转蒸馏法除去溶剂,用乙醇反复洗涤3~5遍后真空干燥,得所述的胺改性聚醚醚酮。
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、聚碳酸酯二元醇或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、聚四亚甲基醚二醇或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或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-羟基丙酸或2-羟基丁酸中的至少一种。
所述稀释剂为丙酮、丁酮、乙酸乙酯、环己酮或N-甲基吡咯烷酮中的至少一种。
所述催化剂为碱性金属羧酸盐、有机金属化合物、含磷化合物或胺化合物;进一步的,优选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、马来酸二丁基锡或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、新戊二醇或二甘醇的至少一种。
所述有机胺扩链剂为乙二胺、二乙烯三胺、己二胺或哌嗪中的至少一种。
所述缩合剂为氯化锌、氯化铝或磷酸中的至少一种;所述甲基化试剂为甲醛、氯甲基甲醚或1-氯-4-(氯甲氧基)丁烷中的至少一种;所述有机溶剂为丙酮、丁酮、醋酸乙酯或环己酮中的至少一种;所述小分子有机胺为乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺或1,6-己二胺中的至少一种。
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。
本发明制得的一种聚醚醚酮改性聚氨酯水性树脂,具有高硬度和贮存稳定性,制成的涂膜具有优异的附着力、耐磨性、耐热水性、耐高温性、耐老化性、抗沾污性、抗辐射性、柔韧性、电绝缘性、耐腐蚀性和自阻燃性,既可单独使用也可以与其它水性树脂共混,用于水性防腐涂料、水性工程涂料、水性耐高温涂料、水性抗静电绝缘涂料、抗辐射涂料、不沾锅涂料。
具体实施方式
下面结合实施例对本发明的一种聚醚醚酮改性聚氨酯水性树脂做进一步的描述。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
一种胺改性聚醚醚酮X,其制备步骤如下:
a)将20.0份浓硫酸加入到反应器中,在0℃下缓慢加入12.0份聚醚醚酮粉末和3.0份氯化锌,搅拌溶液至澄清,然后迅速加入8.0份氯甲基甲醚,继续在0℃下反应2h后停止搅拌,将反应物倒入冰水中得到白色絮状产物,为氯甲基化聚醚醚酮,抽滤,并用蒸馏水将产物反复洗至中性,再用乙醇洗涤3遍后干燥,得氯甲基化的聚醚醚酮;
b)将3.0份氯甲基化的聚醚醚酮溶解于15.0份醋酸乙酯中,搅拌溶解均匀,随后滴加0.4份1,6-己二胺,在1h内滴加完毕,在常温下反应6h,然后用旋转蒸馏法除去溶剂,用乙醇反复洗涤3遍后真空干燥,得所述的胺改性聚醚醚酮X。
实施例2
一种胺改性聚醚醚酮Y,其制备步骤如下:
a)将10.0份浓硫酸加入到反应器中,在0℃下缓慢加入10.0份聚醚醚酮粉末和2.0份磷酸,搅拌溶液至澄清,然后迅速加入6.0份1-氯-4-(氯甲氧基)丁烷,继续在0℃下反应2h后停止搅拌,将反应物倒入冰水中得到白色絮状产物,为氯甲基化聚醚醚酮,抽滤,并用蒸馏水将产物反复洗至中性,再用乙醇洗涤5遍后干燥,得氯甲基化的聚醚醚酮;
b)将2.0份氯甲基化的聚醚醚酮溶解于10.0份丁酮中,搅拌溶解均匀,随后滴加0.1份1,3-丙二胺,在0.8h内滴加完毕,在常温下反应8h,然后用旋转蒸馏法除去溶剂,用乙醇反复洗涤5遍后真空干燥,得所述的胺改性聚醚醚酮Y。
实施例3
一种胺改性聚醚醚酮Z,其制备步骤如下:
a)将12.0份浓硫酸加入到反应器中,在0℃下缓慢加入13.0份聚醚醚酮粉末和4.0份氯化锌,搅拌溶液至澄清,然后迅速加入7.0份甲醛,继续在0℃下反应3.5h后停止搅拌,将反应物倒入冰水中得到白色絮状产物,为氯甲基化聚醚醚酮,抽滤,并用蒸馏水将产物反复洗至中性,再用乙醇洗涤4遍后干燥,得氯甲基化的聚醚醚酮;
b)将2.5份氯甲基化的聚醚醚酮溶解于13.0~15.0份环己酮中,搅拌溶解均匀,随后滴加0.2份乙二胺,在0.5h内滴加完毕,在常温下反应4h,然后用旋转蒸馏法除去溶剂,用乙醇反复洗涤4遍后真空干燥,得所述的胺改性聚醚醚酮Z。
实施例4
一种聚醚醚酮改性聚氨酯水性树脂A,按重量份数计,其成分为:10.0份胺改性聚醚醚酮X、25.0份聚己二酸丁二醇酯二元醇(Mn为2000)、18.0份HDI、3.0份2-羟基丙酸、N-甲基吡咯烷酮12.0份、0.08份二月桂酸二丁基锡、2.0份乙二醇、2.0份三乙胺、0.8份己二胺、120.0份去离子水。
所述聚醚醚酮改性聚氨酯水性树脂A,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HDI、胺改性聚醚醚酮X、聚己二酸丁二醇酯二元醇、2-羟基丙酸,控制温度75℃下反应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℃停止反应;
b)加入N-甲基吡咯烷酮调节体系粘度,在转速为500rpm搅拌下加入乙二醇和二月桂酸二丁基锡进行扩链反应,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90%的去离子水,之后提高转速到1200rpm乳化15min,降低搅拌转速为500rpm;在30min内滴加完己二胺溶液(预先将己二胺溶解到10%的去离子水中),在水相中进行扩链反应1.5h;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A。
实施例5
一种聚醚醚酮改性聚氨酯水性树脂B,按重量份数计,其成分为:15.0份胺改性聚醚醚酮Y、30.0份聚四氢呋喃醚二醇(Mn为1500)、30.0份IPDI、4.5份3-羟基丙酸、16.0份2-吡咯烷酮、0.1份辛酸亚锡、3.0份1,6-己二醇、5.0份三乙胺、1.0份乙二胺、168.0份去离子水。
所述聚醚醚酮改性聚氨酯水性树脂B,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IPDI、胺改性聚醚醚酮、聚四氢呋喃醚二醇、3-羟基丙酸,控制温度90℃下反应2h,取样检测,当所测得的-NCO值达到所规定的理论值时,降温至70℃停止反应;
b)加入2-吡咯烷酮调节体系粘度,在转速为600rpm搅拌下加入小1,6-己二醇和辛酸亚锡进行扩链反应,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10min;接着加入80%的去离子水,之后提高转速到1500rpm乳化15min,降低搅拌转速为600rpm;在30min内滴加完乙二胺溶液(预先将乙二胺溶解到20%的去离子水中),在水相中进行扩链反应1h;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B。
实施例6
一种聚醚醚酮改性聚氨酯水性树脂C,按重量份数计,其成分为:20.0份胺改性聚醚醚酮Z、20.0份聚四亚甲基醚二醇(Mn为3000)、25.0份HDI、6.0份2-羟基丁酸、丙酮15.0份、0.3份马来酸二丁基锡、4.0份1,6-己二醇、4.0份三乙胺、2.0份二乙烯三胺、180.0份去离子水。
所述聚醚醚酮改性聚氨酯水性树脂C,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HDI、改性聚醚醚酮Z、聚四亚甲基醚二醇、2-羟基丁酸,控制温度100℃下反应2h,取样检测,当所测得的-NCO值达到所规定的理论值时,降温至80℃停止反应;
b)加入稀释剂调节体系粘度,在转速为500rpm搅拌下加入1,6-己二醇和马来酸二丁基锡进行扩链反应,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20min;接着加入85%的去离子水,之后提高转速到1300rpm乳化20min,降低搅拌转速为500rpm;在20min内滴加完二乙烯三胺溶液(预先将二乙烯三胺溶解到15%的去离子水中),在水相中进行扩链反应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C。
将本发明实施例中的聚醚醚酮改性聚氨酯水性树脂配制成水性防火涂料与市面上的水性聚氨酯防火涂料(对比例)在相同条件下进行性能对比测试,按照相关标准进行检测,其测试数据如表1所示:
表1聚醚醚酮改性聚氨酯水性防火涂料性能技术指标
尽管本发明已作了详细说明并引用了实施例,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 (8)

1.一种聚醚醚酮改性聚氨酯水性树脂,其特征在于,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;
其中,所述二异氰酸酯为HDI、MDI、IPDI或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-羟基丙酸或2-羟基丁酸中的至少一种;所述稀释剂为丙酮、丁酮或N-甲基吡咯烷酮中的至少一种;所述催化剂为碱性金属羧酸盐、有机金属化合物、含磷化合物或胺化合物中的一种;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、新戊二醇或二甘醇的至少一种;所述有机胺扩链剂为乙二胺、二乙烯三胺、己二胺或哌嗪中的至少一种;
所述胺改性聚醚醚酮,其制备步骤如下:
a)将10.0~20.0份浓硫酸加入到反应器中,在0℃下缓慢加入10.0~15.0份聚醚醚酮粉末和2.0~5.0份缩合剂,搅拌溶液至澄清,然后迅速加入5.0~10.0份甲基化试剂,继续在0℃下反应2~4h后停止搅拌,将反应物倒入冰水中得到白色絮状产物,为氯甲基化聚醚醚酮,抽滤,并用蒸馏水将产物反复洗至中性,再用乙醇洗涤3~5遍后干燥,得氯甲基化的聚醚醚酮;
b)将2.0~3.0份氯甲基化的聚醚醚酮溶解于10.0~15.0份有机溶剂中,搅拌溶解均匀,随后滴加0.1~0.4份的小分子有机胺,在0.5~1h内滴加完毕,在常温下反应4~8h,然后用旋转蒸馏法除去溶剂,用乙醇反复洗涤3~5遍后真空干燥,得所述的胺改性聚醚醚酮。
2.根据权利要求1所述的聚醚醚酮改性聚氨酯水性树脂,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、聚碳酸酯二元醇或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、聚四亚甲基醚二醇或聚环氧丙烷醚二醇中的至少一种,其数均分子量Mn为1000~3000。
3.根据权利要求1所述的聚醚醚酮改性聚氨酯水性树脂,其特征在于,所述缩合剂为氯化锌、氯化铝或磷酸中的至少一种。
4.根据权利要求1所述的聚醚醚酮改性的水性聚氨酯树脂,其特征在于,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、马来酸二丁基锡或二乙酸二丁基锡中的至少一种。
5.根据权利要求1所述的聚醚醚酮改性聚氨酯水性树脂,其特征在于,所述甲基化试剂为甲醛、氯甲基甲醚或1-氯-4-(氯甲氧基)丁烷中的至少一种。
6.根据权利要求1所述的聚醚醚酮改性聚氨酯水性树脂,其特征在于,所述有机溶剂为丙酮、丁酮、乙酸乙酯、环己酮中的至少一种。
7.根据权利要求1所述的聚醚醚酮改性聚氨酯水性树脂,其特征在于,所述小分子有机胺为乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺或1,6-己二胺中的至少一种。
8.一种如权利要求1所述的聚醚醚酮改性聚氨酯水性树脂的制备方法,其特征在于,所述制备步骤如下:
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)将有机胺扩链剂预先溶解到10~20%的去离子水中;
d)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。
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