CN110330634A - 一种新型的耐水解超支化含氟水性聚氨酯的制备方法 - Google Patents
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Abstract
本发明公开了一种新型的耐水解超支化含氟水性聚氨酯的制备方法,包括如下步骤:(1)第一步是合成的线性水性聚氨酯;(2)先用三胺单体进行超支化处理,在通过迈克尔加成反应将甲基丙烯酸六氟丁酯接枝上去,本发明综合了超支化和氟改性两种优点:通过氟改性赋予其优异的耐水性,超支化则降低乳液粘度,提高了其成膜性,引入了脲键,对其力学性能和耐热性提升,并进一步加强耐水性,常温下较短时间反应即可完成,综合了超支化和氟改性两种优点,并且氟的利用率更高,少量含氟单体即可明显提高耐水性。
Description
技术领域
本发明涉及化学涂料技术领域,具体为一种新型的耐水解超支化含氟水性聚氨酯的制备方法。
背景技术
近年来由于环保要求日益严格,降低涂料中的挥发性有机化合物(VOC)含量变得重要起来,因而水性聚氨酯(WPU)涂层引起了人们的关注,WPU用阴离子盐进行水性化,以水作为溶剂,因而具有低VOC、无毒、无污染、不燃等优点,但与此同时,其也具有耐水性差的缺点,这使得其长期使用后涂层的粘附性、耐磨性等性能下降较快,因而需要对WPU进行改性。
有机氟一般表面能低、化学键能较高,用其改性能显著提高WPU的耐水性和热稳定性等,相比硅改性而言,氟改性对WPU的改善更明显,较低含量的氟即可显著提高其耐水性,并且不易对WPU的原有结构造成影响。
现阶段合成氟改性水性聚氨酯的方法一般是在线性水性聚氨酯预聚体末端用丙烯酸羟乙酯等进行双键封端,然后通过自由基聚合的方法将含氟丙烯酸酯单体引入到聚氨酯中,这种方法的缺点在于自由基聚合反应需要较高的温度,并且反应时间较长,且聚氨酯分子链较长,含氟单体容易自聚。
发明内容
本发明的目的在于提供一种新型的耐水解超支化含氟水性聚氨酯的制备方法,以解决上述背景技术中提出的问题。
为实现上述目的,本发明提供如下技术方案:一种新型的耐水解超支化含氟水性聚氨酯的制备方法,包括如下步骤:
(1)线性水性聚氨酯的合成:将聚四氢呋喃二醇(PTMG2000)在真空度为-0.095MPa、130℃下真空除水2h,然后放入干燥塔干燥保存,装有冷凝回流装置、机械搅拌器并通有N2的250ml四口瓶中加入经过除水处理的0.00125mol(2.5g)PTMG2000,0.00225mol(0.3018g)二羟甲基丙酸(DMPA),加入溶剂并加热搅拌至温度达到75℃,加入0.00525mol(1.1670g)异佛尔酮二异氰酸酯(IPDI)与催化剂,此时NCO/OH=1.5:1,在此温度下反应3h后,生成线性水性聚氨酯;
(2)超支化含氟水性聚氨酯的制备:将四口瓶移至室温下,加入0.00175mol(0.7700g)的聚醚胺,搅拌反应约2h,待超支化反应完成后,依次加入总反应物质量分数的0%、1%、3%、%5、7%、10%的甲基丙烯酸六氟丁酯(HFBMA)继续室温下反应,至溶液变为深黄色,加入三乙胺(与DMPA等摩尔量)与20ml去离子水,充分搅拌0.5h,然后在真空度为-0.095MPa、常温下旋蒸除去丙酮,即可得到超支化含氟水性聚氨酯(HFWPU)。
优选的,所述溶剂为40ml丙酮和5mlN-甲基吡咯烷酮(NMP)。
优选的,所述线性水性聚氨酯的合成中的催化剂为0.3g的二月桂酸二丁基锡(DBTDL)。
与现有技术相比,本发明的有益效果是:
1、综合了超支化和氟改性两种优点:通过氟改性赋予其优异的耐水性,超支化则降低乳液粘度,提高了其成膜性,引入了脲键,对其力学性能和耐热性提升,并进一步加强耐水性。
2、两种改性在常温下即可进行:氨基与异氰酸根在常温下即可快速反应,而双键与氨基的迈克尔加成反应属于点击化学,常温下也能容易进行,并且由于没有使用引发剂,含氟单体不会自聚,载入量更高。
我们这种改性方法合成条件更加简便,常温下较短时间反应即可完成,综合了超支化和氟改性两种优点,并且氟的利用率更高,少量含氟单体即可明显提高耐水性。
附图说明
图1为为HFWPU的合成路线图;
图2为HFWPU-5%的红外光谱;
图3为HFWPU-5%的XPS曲线;
图4为HFWPU的吸水率曲线。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明提供一种技术方案:
实施例1
一种新型的耐水解超支化含氟水性聚氨酯的制备方法,包括如下步骤:
(1)线性水性聚氨酯的合成:将聚四氢呋喃二醇(PTMG2000)在真空度为-0.095MPa、130℃下真空除水2h,然后放入干燥塔干燥保存,装有冷凝回流装置、机械搅拌器并通有N2的250ml四口瓶中加入经过除水处理的0.00125mol(2.5g)PTMG2000,0.00225mol(0.3018g)二羟甲基丙酸(DMPA),加入溶剂并加热搅拌至温度达到75℃,加入0.00525mol(1.1670g)异佛尔酮二异氰酸酯(IPDI)与催化剂,此时NCO/OH=1.5:1,在此温度下反应3h后,生成线性水性聚氨酯。
(2)超支化含氟水性聚氨酯的制备:将四口瓶移至室温下,加入0.00175mol(0.7700g)的聚醚胺,搅拌反应约2h,待超支化反应完成后,依次加入总反应物质量分数的0%、1%、3%、%5、7%、10%的甲基丙烯酸六氟丁酯(HFBMA)继续室温下反应,至溶液变为深黄色,加入三乙胺(与DMPA等摩尔量)与20ml去离子水,充分搅拌0.5h,然后在真空度为-0.095MPa、常温下旋蒸除去丙酮,即可得到超支化含氟水性聚氨酯(HFWPU)。
作为本发明更进一步的改进,溶剂为40ml丙酮和5mlN-甲基吡咯烷酮(NMP),且线性水性聚氨酯的合成中的催化剂为0.3g的二月桂酸二丁基锡(DBTDL),能够加速线性水性聚氨酯的反应生成。
实验数据:
实施例2
一种新型的耐水解超支化含氟水性聚氨酯的制备方法,包括如下步骤:
(1)线性水性聚氨酯的合成:将聚四氢呋喃二醇(PTMG2000)在真空度为-0.095MPa、130℃下真空除水2h,然后放入干燥塔干燥保存,装有冷凝回流装置、机械搅拌器并通有N2的250ml四口瓶中加入经过除水处理的0.0025mol(5g)PTMG2000,0.00225mol(0.3018g)二羟甲基丙酸(DMPA),加入溶剂并加热搅拌至温度达到85℃,加入1.355g异佛尔酮二异氰酸酯(IPDI)与催化剂,在此温度下反应3h后,生成线性水性聚氨酯。
(2)超支化含氟水性聚氨酯的制备:将四口瓶移至室温下,加入1.3g的聚醚胺,搅拌反应约2h,待超支化反应完成后,依次加入总反应物质量分数的0%、1%、3%、%5、7%、10%的甲基丙烯酸六氟丁酯(HFBMA)继续室温下反应,至溶液变为深黄色,加入三乙胺(与DMPA等摩尔量)与30ml去离子水,充分搅拌0.5h,然后在真空度为-0.095MPa、常温下旋蒸除去丙酮,即可得到超支化含氟水性聚氨酯(HFWPU),此种实施例所得到的超支化含氟水性聚氨酯(HFWPU)含水量较多。
实验数据:
以上对本发明实施例所提供的技术方案进行了详细介绍,本文中应用了具体个例对本发明实施例的原理以及实施方式进行了阐述,以上实施例的说明只适用于帮助理解本发明实施例的原理;同时,对于本领域的一般技术人员,依据本发明实施例,在具体实施方式以及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本发明的限制。
Claims (3)
1.一种新型的耐水解超支化含氟水性聚氨酯的制备方法,其特征在于包括如下步骤:
(1)线性水性聚氨酯的合成:将聚四氢呋喃二醇(PTMG2000)在真空度为-0.095MPa、130℃下真空除水2h,然后放入干燥塔干燥保存,装有冷凝回流装置、机械搅拌器并通有N2的250ml四口瓶中加入经过除水处理的0.00125mol(2.5g)PTMG2000,0.00225mol(0.3018g)二羟甲基丙酸(DMPA),加入溶剂并加热搅拌至温度达到75℃,加入0.00525mol(1.1670g)异佛尔酮二异氰酸酯(IPDI)与催化剂,此时NCO/OH=1.5:1,在此温度下反应3h后,生成线性水性聚氨酯;
(2)超支化含氟水性聚氨酯的制备:将四口瓶移至室温下,加入0.00175mol(0.7700g)的聚醚胺,搅拌反应约2h,待超支化反应完成后,依次加入总反应物质量分数的0%、1%、3%、%5、7%、10%的甲基丙烯酸六氟丁酯(HFBMA)继续室温下反应,至溶液变为深黄色,加入三乙胺(与DMPA等摩尔量)与20ml去离子水,充分搅拌0.5h,然后在真空度为-0.095MPa、常温下旋蒸除去丙酮,即可得到超支化含氟水性聚氨酯(HFWPU)。
2.根据权利要求1所述的一种新型的耐水解超支化含氟水性聚氨酯的制备方法,其特征在于:所述溶剂为40ml丙酮和5mlN-甲基吡咯烷酮(NMP)。
3.根据权利要求1所述的一种新型的耐水解超支化含氟水性聚氨酯的制备方法,其特征在于:所述线性水性聚氨酯的合成中的催化剂为0.3g的二月桂酸二丁基锡(DBTDL)。
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