CN110862508B - 三嗪基含氟扩链剂改性聚氨酯乳液的制备方法 - Google Patents
三嗪基含氟扩链剂改性聚氨酯乳液的制备方法 Download PDFInfo
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Abstract
本发明涉及聚氨酯涂层技术领域,具体涉及一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法。为解决如何利用有机氟改性水性聚氨酯,使其具有优异的疏水性能,同时降低制备成本的问题。本发明采用的制备方法为1)三嗪基含氟扩链剂的合成;2)‑NCO封端的含氟聚氨酯预聚体的合成;3)三嗪基含氟扩链剂改性聚氨酯的制备,4)三嗪基含氟扩链剂改性聚氨酯乳液的制备。
Description
技术领域
本发明涉及聚氨酯涂层技术领域,具体涉及一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法。
背景技术
随着人们环保理念和生活质量的提高,水性聚氨酯因其环境友好、应用范围广、成本低廉等优势,逐渐取代了溶剂型聚氨酯。然而水性聚氨酯以水为介质,同时聚氨酯分子链中含有-COOH、-OH等亲水基团,使得其成膜后的耐水性能变差,使用性能较差。有机氟中的C-F键的键能大,稳定性高,而且表面能很低,所以含氟材料表现出较好的疏水性和疏油性。在水性聚氨酯中引入含氟基团或链段后,不仅具有传统聚氨酯的优良特性,还可以获得优异的疏水性能,使其更广泛的应用在各个领域中。
目前对有机氟改性水性聚氨酯材料的研究众多,按照引入水性聚氨酯的方式主要分为两类:一、以含氟扩链剂引入WPU分子链中;二、以含氟封端剂接枝在WPU分子链末端。
一、含氟扩链剂改性水性聚氨酯:
孙常青等采用异佛尔酮二异氰酸酯、全氟己基乙醇和三羟甲基丙烷自制含氟二元醇(IT-TEOH-6),结构如下:以此制备了氟改性UV固化超支化水性聚氨酯(FWPU)。
二、含氟封端剂改性水性聚氨酯:
Zhang等先以全氟烷基乙醇对二苯甲烷二异氰酸酯进行改性,然后将其作为封端剂接枝在制备好的端羟基聚氨酯分子上,制备出了一种疏水氟化聚氨酯。
Khayet等以低聚氟醇(FAE)作为封端剂,制备出一种含氟聚氨酯(FPA),结构式如下:
上述两种方法方案中,含氟烷基以扩链剂或者封端剂的方式引入水性聚氨酯中,这种单一的改性方式,可能会在水性聚氨酯成膜时,含氟基团不能均匀且致密的分布在胶膜的表面,使其对聚氨酯膜的覆盖和保护作用不够充分,所以胶膜的疏水性能未能达到预期效果;并且有机氟的价格昂贵,如果为提高疏水性能而盲目使用,使得成本很高。
发明内容
有鉴于此,本发明为解决如何利用有机氟改性水性聚氨酯,使其具有优异的疏水性能,同时降低制备成本的问题,提供一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法。
为解决现有技术存在的问题,本发明的技术方案是:三嗪基含氟扩链剂改性聚氨酯乳液的制备方法,其特征在于:所述方法包括以下步骤:
1)三嗪基含氟扩链剂的合成:
以三聚氰氯和有机氟醇为原料,丙酮和水的混合液为溶剂,NaOH为缚酸剂,在冰浴且搅拌的条件下,反应4h,然后升温至45℃,加入乙醇胺和NaOH,继续反应5h,再次升温至95℃,加入乙醇胺和NaOH,反应8h,制得三嗪基含氟扩链剂;
2)-NCO封端的含氟聚氨酯预聚体的合成:
以异佛尔酮二异氰酸酯和聚酯或聚醚二元醇为原料,二月桂酸二丁基锡为催化剂,在80℃下反应1h,然后将步骤1)所得的三嗪基含氟扩链剂和2,2-二羟甲基丙酸按照比例溶解于四氢呋喃后加入体系,反应2.5h,制得-NCO封端的含氟聚氨酯预聚体;
3)三嗪基含氟扩链剂改性聚氨酯的制备:
在温度为80℃的条件下,将全氟己基乙醇缓慢滴加至上述反应体系,加热搅拌3h,对聚氨酯预聚体进行单侧封端;再缓慢滴加交联剂,反应1h,制得三嗪基含氟扩链剂改性聚氨酯;
4)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将体系温度降至40℃,加入三乙胺中和0.5h,然后在高速搅拌的条件下,缓慢加入去离子水,分散乳化1h后,在50℃、-0.1Mpa条件下旋蒸0.5h除去溶剂,制得三嗪基含氟扩链剂改性聚氨酯乳液。
进一步,步骤1)中的有机氟醇为六氟异丙醇、八氟戊醇、全氟己基乙醇中的一种,且均为单羟基的有机氟化合物。
进一步,步骤2)中的聚酯或聚醚二元醇为聚四氢呋喃、聚己内酯二醇中的一种。
进一步,步骤2)中2,2-二羟甲基丙酸与三嗪基含氟扩链剂的摩尔比为1~3。
进一步,步骤3)中的交联剂为三羟甲基丙烷、季戊四醇中的一种。
与现有技术相比,本发明的优点如下:
1、本发明制备的三嗪基含氟扩链剂引入聚氨酯主链中后,有利于水性聚氨酯在成膜时含氟链段的均匀分布;同时接枝在聚氨酯分子链端的氟醇,其所处位置有利于成膜过程中含氟链段的迁移,具有低量高效的特点;并且两者的协同改性作用使得含氟基团在胶膜表面的铺展、覆盖和保护作用更加充分,赋予水性聚氨酯胶膜更加优异的疏水性能;
2、本发明中聚氨酯分子结构内引入的三嗪环具有较高的热稳定性,不易被破坏,同时该环又是含氮杂环,将其引入聚合物链段中,可在一定程度上提高聚氨酯胶膜的热稳定性;加入的内交联剂可以提高水性聚氨酯胶膜的致密程度,提高了胶膜机械性能的同时,有利于疏水性和耐热稳定性的提高;
3、本发明可有效降低含氟单体的用量,同时可以赋予水性聚氨酯优异的胶膜防水性能。
具体实施方式
一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法包括以下步骤:
(1)三嗪基含氟扩链剂的合成:
冰浴条件下,向含有丙酮和水的混合液(m丙酮/m水=1.3:1)的烧瓶中加入三聚氰氯,搅拌的同时缓慢滴加有机氟醇的丙酮溶液和NaOH水溶液,保持体系温度为0~5℃,反应4h;然后将体系温度升至45℃,再同时缓慢滴加乙醇胺的丙酮溶液和NaOH的水溶液,反应5h;继续升温,当体系温度达到95℃时,同时滴加乙醇胺的丙酮溶液和NaOH水溶液,再反应8h,反应结束,待体系恢复到室温,过滤并用丙酮和水多次洗涤滤饼,经过真空干燥得到三嗪基含氟扩链剂;
上述有机氟醇为六氟异丙醇、八氟戊醇、全氟己基乙醇中的一种,且均为单羟基的有机氟化合物。
(2)-NCO封端的含氟聚氨酯预聚体的合成:
以异佛尔酮二异氰酸酯和聚酯或聚醚二元醇为原料,二月桂酸二丁基锡为催化剂,在80℃下反应1h,然后将步骤(1)所得的三嗪基含氟扩链剂和2,2-二羟甲基丙酸按一定的摩尔比例溶解于四氢呋喃后加入,反应2.5h,即制得-NCO封端的含氟聚氨酯预聚体;
上述聚酯或聚醚二元醇为聚四氢呋喃、聚己内酯二醇中的一种。
上述DMPA和CC-F的摩尔比例范围为(nDMPA:nCC-F=1-3)
(3)三嗪基含氟扩链剂改性聚氨酯的制备:
在80℃的条件下,将全氟己基乙醇的丙酮溶液缓慢滴加至上述反应体系,加热搅拌3h,对聚氨酯预聚体进行单侧封端;再缓慢滴加交联剂的丙酮溶液,反应1h,制得三嗪基含氟扩链剂改性聚氨酯;
上述交联剂为三羟甲基丙烷、季戊四醇中的一种。
(4)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将体系温度降至40℃,加入三乙胺中和0.5h,然后在高速搅拌的条件下,缓慢加入去离子水,分散乳化1h后,在50℃、-0.1Mpa条件下旋蒸0.5h除去溶剂,制得三嗪基含氟扩链剂改性聚氨酯乳液。
步骤(1)中合成三嗪基含氟扩链剂的反应方程式如下:
步骤(2-3)中合成三嗪基含氟扩链剂改性聚氨酯乳液的反应方程式如下:
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实例中的试剂在使用前均需进行干燥处理。
实施例一:
一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法为:
(1)三嗪基含氟扩链剂的合成:
在1℃条件下,准确称取1.54g(0.0084mol)三聚氰氯加入含有6g的丙酮/水的混合液(m丙酮/m水=1.3:1)的三口烧瓶中,然后将3.04g(0.0084mol)全氟己基乙醇(S104)溶解于6g的丙酮中,与3.50g(0.0088mol)10%的NaOH水溶液同时缓慢滴加到上述体系中,约2h滴加完毕,滴完继续反应2h;反应完后,将温度升至45℃,向反应体系中缓慢滴加0.51g(0.0084mol)乙醇胺的丙酮溶液和3.34g(0.0084mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应3.5h。继续升温,当体系温度达到95℃时,同时滴加0.51g(0.0084mol)乙醇胺的丙酮溶液和3.34g(0.0084mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应6.5h。反应结束,待体系恢复到室温,过滤并用丙酮和水多次洗涤滤饼后,经过真空干燥得到三嗪基含氟扩链剂(CC-F);
(2)-NCO封端的含氟聚氨酯预聚体的合成:
准确称取12g(0.0540mol)异佛尔酮二异氰酸酯(IPDI)和20g(0.0200mol)聚己内酯二醇(PCL-1000),在冷凝回流的条件下进行加热搅拌,待体系温度达到80℃,加二月桂酸二丁基锡(DBTDL)三滴,反应1h,然后将4.68g(0.0084mol)三嗪基含氟扩链剂和2.24g(0.0167mol)2,2-二羟甲基丙酸(DMPA)溶解于四氢呋喃后加入体系中,反应2.5h,制得-NCO封端的含氟聚氨酯预聚体;
(3)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将3.28g(0.0090mol)的S104溶于适量丙酮中,滴加到步骤(2)制备的聚氨酯预聚体中,在80℃下反应2h;再将0.41g(0.0030mol)三羟甲基丙烷(TMP)溶解于丙酮中滴加至反应体系中,反应2h,使反应进行直至-NCO基团消失,通过二正丁胺滴定法测定。再降温到40℃,加一定量丙酮稀释降粘,并加入1.69g(0.0167mol)TEA,中和0.5h,然后缓慢滴加去离子水并高速搅拌1h,制得三嗪基含氟扩链剂改性聚氨酯乳液(CC-FPU)。
实施例二:
一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法为:
(1)三嗪基含氟扩链剂的合成:
在2℃条件下,准确称取2.31g(0.0125mol)三聚氰氯加入含有8g的丙酮/水的混合液(m丙酮/m水=1.3:1)的三口烧瓶中,然后将2.91g(0.0125mol)八氟戊醇(OFP)溶解于6g的丙酮中,与5.25g(0.0132mol)10%的NaOH水溶液同时缓慢滴加到上述体系中,约2h滴加完毕,滴完继续反应2h;反应完后,将温度升至45℃,向反应体系中缓慢滴加0.77g(0.0125mol)乙醇胺的丙酮溶液和5.00g(0.0125mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应3.5h。继续升温,当体系温度达到95℃时,同时滴加0.77g(0.0125mol)乙醇胺的丙酮溶液和5.00g(0.0125mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应6.5h。反应结束,待体系恢复到室温,过滤并用丙酮和水多次洗涤滤饼后,经过真空干燥得到三嗪基含氟扩链剂(CC-F);
(2)-NCO封端的含氟聚氨酯预聚体的合成:
准确称取12g(0.0540mol)异佛尔酮二异氰酸酯(IPDI)和20g(0.0200mol)聚四氢呋喃(PTHF),在冷凝回流的条件下进行加热搅拌,待体系温度达到80℃,加二月桂酸二丁基锡(DBTDL)三滴,反应1h,然后将5.39g(0.0125mol)三嗪基含氟扩链剂和1.68g(0.0125mol)2,2-二羟甲基丙酸(DMPA)溶解于四氢呋喃后加入体系中,反应2.5h,制得-NCO封端的含氟聚氨酯预聚体;
(3)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将3.28g(0.0090mol)的S104溶于适量丙酮中,滴加到步骤(2)制备的聚氨酯预聚体中,在80℃下反应2h;再将0.31g(0.0023mol)季戊四醇(PE)溶解于丙酮中滴加至反应体系中,反应2h,使反应进行直至-NCO基团消失,通过二正丁胺滴定法测定。再降温到40℃,加一定量丙酮稀释降粘,并加入1.27g(0.0125mol)TEA,中和0.5h,然后缓慢滴加去离子水并高速搅拌1h,制得三嗪基含氟扩链剂改性聚氨酯乳液(CC-FPU)。
实施例三:
一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法为:
(1)三嗪基含氟扩链剂的合成:
在3℃条件下,准确称取1.54g(0.0084mol)三聚氰氯加入含有6g的丙酮/水的混合液(m丙酮/m水=1.3:1)的三口烧瓶中,然后将1.41g(0.0084mol)六氟异丙醇(HFIP)溶解于3g的丙酮中,与3.50g(0.0088mol)10%的NaOH水溶液同时缓慢滴加到上述体系中,约2h滴加完毕,滴完继续反应2h,反应完后,将温度升至45℃,向反应体系中缓慢滴加0.51g(0.0084mol)乙醇胺的丙酮溶液和3.34g(0.0084mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应3.5h。继续升温,当体系温度达到95℃时,同时滴加0.51g(0.0084mol)乙醇胺的丙酮溶液和3.34g(0.0084mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应6.5h。反应结束,待体系恢复到室温,过滤并用丙酮和水多次洗涤滤饼后,经过真空干燥得到三嗪基含氟扩链剂(CC-F);
(2)-NCO封端的含氟聚氨酯预聚体的合成:
准确称取12g(0.0540mol)异佛尔酮二异氰酸酯(IPDI)和20g(0.0200mol)聚己内酯二醇(PCL-1000),在冷凝回流的条件下进行加热搅拌,待体系温度达到80℃,加二月桂酸二丁基锡(DBTDL)三滴,反应1h,然后将3.05g(0.0084mol)三嗪基含氟扩链剂和2.24g(0.0167mol)2,2-二羟甲基丙酸(DMPA)溶解于四氢呋喃后加入体系中,反应2.5h,制得-NCO封端的含氟聚氨酯预聚体;
(3)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将3.28g(0.0090mol)的S104溶于适量丙酮中,滴加到步骤(2)制备的聚氨酯预聚体中,在80℃下反应2h;再将0.41g(0.0030mol)三羟甲基丙烷(TMP)溶解于丙酮中滴加至反应体系中,反应2h,使反应进行直至-NCO基团消失,通过二正丁胺滴定法测定。再降温到40℃,加一定量丙酮稀释降粘,并加入1.69g(0.0167mol)TEA,中和0.5h,然后缓慢滴加去离子水并高速搅拌1h,制得三嗪基含氟扩链剂改性聚氨酯乳液(CC-FPU)。
实施例四:
一种三嗪基含氟扩链剂改性聚氨酯乳液的制备方法为:
(1)三嗪基含氟扩链剂的合成:
在5℃条件下,准确称取2.31g(0.0125mol)三聚氰氯加入含有8g的丙酮/水的混合液(m丙酮/m水=1.3:1)的三口烧瓶中,然后将4.55g(0.0125mol)S104溶解于9g的丙酮中,与5.25g(0.0132mol)10%的NaOH水溶液同时缓慢滴加到上述体系中,约2h滴加完毕,滴完继续反应2h,反应完后,将温度升至45℃,向反应体系中缓慢滴加0.77g(0.0125mol)乙醇胺的丙酮溶液和5.00g(0.0125mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应3.5h。继续升温,当体系温度达到95℃时,同时滴加0.77g(0.0125mol)乙醇胺的丙酮溶液和5.00g(0.0125mol)的10%的NaOH水溶液,滴加约1.5h,并恒温反应6.5h。反应结束,待体系恢复到室温,过滤并用丙酮和水多次洗涤滤饼后,经过真空干燥得到三嗪基含氟扩链剂(CC-F);
(2)-NCO封端的含氟聚氨酯预聚体的合成:
准确称取12g(0.0540mol)异佛尔酮二异氰酸酯(IPDI)和20g(0.0200mol)聚四氢呋喃(PTHF),在冷凝回流的条件下进行加热搅拌,待体系温度达到80℃,加二月桂酸二丁基锡(DBTDL)三滴,反应1h,然后将7.02g(0.0125mol)三嗪基含氟扩链剂和1.68g(0.0125mol)2,2-二羟甲基丙酸(DMPA),溶解于丙酮后加入体系中,反应2.5h,制得-NCO封端的含氟聚氨酯预聚体;
(3)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将3.28g(0.0090mol)的S104溶于适量丙酮中,滴加到步骤(2)制备的聚氨酯预聚体中,在80℃下反应2h;再将0.31g(0.0023mol)季戊四醇(PE)溶解于丙酮中滴加至反应体系中,反应2h,使反应进行直至-NCO基团消失,通过二正丁胺滴定法测定。再降温到40℃,加一定量丙酮稀释降粘,并加入1.27g(0.0125mol)TEA,中和0.5h,然后缓慢滴加去离子水并高速搅拌1h,制得三嗪基含氟扩链剂改性聚氨酯乳液(CC-FPU)。
以上所述仅是本发明的优选实施例,并非用于限定本发明的保护范围,应当指出,对本技术领域的普通技术人员在不脱离本发明原理的前提下,对其进行若干改进与润饰,均应视为本发明的保护范围。
Claims (4)
1.三嗪基含氟扩链剂改性聚氨酯乳液的制备方法,其特征在于:所述方法包括以下步骤:
1)三嗪基含氟扩链剂的合成:
以三聚氰氯和有机氟醇为原料,丙酮和水的混合液为溶剂,NaOH为缚酸剂,在冰浴且搅拌的条件下,反应4h,然后升温至45℃,加入乙醇胺和NaOH,继续反应5h,再次升温至95℃,加入乙醇胺和NaOH,反应8h,制得三嗪基含氟扩链剂;
所述的有机氟醇为六氟异丙醇、八氟戊醇、全氟己基乙醇中的一种;
2)-NCO封端的含氟聚氨酯预聚体的合成:
以异佛尔酮二异氰酸酯和聚酯或聚醚二元醇为原料,二月桂酸二丁基锡为催化剂,在80℃下反应1h,然后将步骤1)所得的三嗪基含氟扩链剂和2,2-二羟甲基丙酸按照比例溶解于四氢呋喃后加入体系,反应2.5h,制得-NCO封端的含氟聚氨酯预聚体;
3)三嗪基含氟扩链剂改性聚氨酯的制备:
在温度为80℃的条件下,将全氟己基乙醇缓慢滴加至上述反应体系,加热搅拌3h,对聚氨酯预聚体进行单侧封端;再缓慢滴加交联剂,反应1h,制得三嗪基含氟扩链剂改性聚氨酯;
4)三嗪基含氟扩链剂改性聚氨酯乳液的制备:
将体系温度降至40℃,加入三乙胺中和0.5h,然后在高速搅拌的条件下,缓慢加入去离子水,分散乳化1h后,在50℃、-0.1Mpa条件下旋蒸0.5h除去溶剂,制得三嗪基含氟扩链剂改性聚氨酯乳液。
2.根据权利要求1所述的三嗪基含氟扩链剂改性聚氨酯乳液的制备方法,其特征在于:所述步骤2)中的聚酯或聚醚二元醇为聚四氢呋喃、聚己内酯二醇中的一种。
3.根据权利要求1或2所述的三嗪基含氟扩链剂改性聚氨酯乳液的制备方法,其特征在于:所述步骤2)中2,2-二羟甲基丙酸与三嗪基含氟扩链剂的摩尔比为1~3。
4.根据权利要求3所述的三嗪基含氟扩链剂改性聚氨酯乳液的制备方法,其特征在于:所述步骤3)中的交联剂为三羟甲基丙烷、季戊四醇中的一种。
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