CN106349452A - 端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法 - Google Patents
端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种皮革涂饰剂技术领域,具体涉及一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法。本发明为克服现有溶剂型聚氨酯存在的安全隐患、易污染环境和成本高及水性聚氨酯的耐水性差等问题,提出一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法方法:首先将氨基改性纳米二氧化硅与AB2单体N,N‑二羟乙基‑3‑胺基‑丙酸甲酯反应制备超支化纳米杂化聚合物;其次,将聚酯或聚醚多元醇与异氰酸酯进行混合,搅拌反应,加入羧酸型扩链剂反应,再加入有机氟醇部分封端,之后,加入有机胺中和,加入丙酮做溶剂稀释;再将部分封端的聚氨酯预聚体与超支化纳米杂化聚合物混合,搅拌反应;最后抽真空回收丙酮,加水高速搅拌分散即可。
Description
技术领域
本发明涉及一种皮革涂饰剂技术领域,具体涉及一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法。
背景技术
天然皮革以其时尚的外观、优异的吸湿透气等性能备受消费者的青睐。然而,日常生活中油污、食品饮料、染料等不断的侵扰严重影响了它的应用,防水、防污和自清洁性能自然成为高端皮革制品的一大需求。皮革防水可用防水涂饰剂对皮革表面进行喷涂,方法简单,效果显著。近年来,聚氨酯(PU)皮革涂饰剂以其优良的性能引起了皮革界的广泛重视。而与溶剂型聚氨酯相比,水性聚氨酯具有无毒、无污染、运输方便、安全防火等优点,因而有逐渐取代溶剂型聚氨酯的趋势。但由于在合成过程中引入较多的亲水性扩链剂,导致水性聚氨酯产品的耐水性较差。因而如何改善水性聚氨酯涂饰剂的耐水性成为当前研究的热点。
碳氟化合物具有优异的耐热和耐化学稳定性、拒水拒油性和低表面能,常用于各种材料的疏水改性。然而,含氟单体价格昂贵,使得含氟聚合物的应用成本居高不下。目前,关于有机氟改性聚氨酯的文献报道多利用嵌段或接枝的方式把有机氟链段引入线型聚氨酯分子中。如汪武以聚四氢呋喃和IPDI为原料,以自制的含氟二元醇为扩链剂合成了嵌端有机氟改性聚氨酯乳液,改善了PU胶膜的疏水性[聚氨酯工业,2007,22:21-23]。由于有机氟链段以嵌端方式存在于聚氨酯链节中,它不利于含氟基团的表面迁移。因此,改性后乳胶膜表面的水静态接触角仅为93.5°。显然这还达不到显著地改善水性聚氨酯膜耐水性的目的。又如Tang利用氟醇改性-NCO封端的聚氨酯预聚体制得大分子端氟烷基聚氨酯表面处理剂(SMMs)[Journal of Applied Polymer Science,1996,62:1133-1145],但为获得较好的性能,需要使用约40wt%的长链全氟烷基醇,一方面,长链全氟烷基存在生物积累和对环境的危害;另一方面,这也会造成高昂的应用成本。因而有机氟改性聚氨酯的研究仍有更大的改进空间。超支化聚合物具有多端基、低熔点、流变性好、溶解性能优良和反应活性高等特点,如能通过改性将氟烷基引入超支化聚合物分子末端制备端氟烷基超支化聚合物。这样处于分子末端的含氟基团在应用于基质表面后的成膜过程中更易于向表面迁移,因而在改善疏水疏油效果上更加有效,可降低其应用成本。此外,依据仿生超疏水研究的理论基础,微纳米二元粗糙结构与低表面能物质相结合是构筑防污自清洁界面的基础。因此,在超支化聚合物中引入纳米粒子可增加处理后基质表面的粗糙度,进一步增强其防污自清洁性能。
发明内容
本发明为克服现有溶剂型聚氨酯存在有严重安全隐患、易污染环境和成本高以及水性聚氨酯的耐水性差等问题,提供一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法。
为实现上述目的,本发明采用的技术方案为:一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于:所述方法包括以下步骤:
(1)端羟基超支化纳米杂化聚合物的合成:室温下在超声波分散仪中将纳米SiO2均匀分散于丙酮中,然后将氨基硅烷偶联剂加入分散液中,继续超声分散均匀,然后将分散液转移至三口烧瓶,在60~80℃下加热搅拌反应10~20h,然后加入AB2单体N,N-二羟乙基-3-胺基-丙酸甲酯反应2~3h,制得端羟基超支化纳米杂化聚合物;
(2)NCO封端的聚氨酯预聚体的合成:将聚酯或聚醚多元醇和异氟尔酮二异氰酸酯以1:1.1~1.5的摩尔比混合,加混合物质量0.1~1.5%的二月桂酸二丁基锡做催化剂,在N2保护下,升温至60~90℃,持续搅拌反应1~2h后,加羧酸型扩链剂进行扩链,同时加入丙酮,在50~70℃下保温反应2~4h,制得NCO封端的聚氨酯预聚体PU;
(3)端氟烷基超支化纳米杂化聚氨酯的合成:在温度为60~80℃的条件下,将有机氟醇滴入步骤(2)所得的NCO封端的聚氨酯预聚体的三口烧瓶内,搅拌反应3~5h;再将步骤(1)所得的端羟基超支化纳米杂化聚合物按摩尔比为1:2的比例加入上述反应体系,在60~80℃的条件下,持续反应3~5h至反应完全;
(4)端氟烷基超支化纳米杂化聚氨酯乳液的制备:将步骤(3)的体系温度降至40~50℃,加有机胺中和并加水高速搅拌分散,然后在20~50℃下旋蒸半小时除去溶剂,制得固含量为30~50%的端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂。
步骤(1)中的氨基硅烷偶联剂为氨丙基三甲氧基硅烷或氨丙基三乙氧基硅烷。
步骤(1)中的超支化纳米杂化聚合物为端羟基超支化纳米杂化聚合物。
步骤(2)中的聚酯或聚醚多元醇为聚己二酸丁二醇酯、聚乙二醇中的一种。
于步骤(2)中的羧酸型扩链剂为2,2-二羟甲基丙酸或2,2-二羟甲基丁酸。
步骤(3)中的有机氟醇为单官能团,选自全氟烷基乙醇[CF3(CF2)nCH2CH2OH](0≤n≤6)中的一种,用于超支化聚氨酯末端接枝。
步骤(4)中的有机胺为三乙胺或二乙胺,其用量与羧酸型扩链剂的物质的量相等。
与现有技术相比,本发明具有如下优点和效果:
1、低成本改善水性聚氨酯的耐水性:本发明以氨基改性纳米SiO2为核合成出端羟基超支化纳米杂化聚合物,再以聚氨酯预聚体为桥将有机氟醇连接到超支化聚氨酯的末端,该结构有利于氟烃基在超支化聚氨酯成膜过程中更易于向表面迁移,因而可大大减少有机氟醇的引入量,降低成本;其次,纳米SiO2的引入又会提高膜表面的粗糙度,根据仿生超疏水的理论基础,从而进一步提高水性聚氨酯膜的耐水性。
2、本发明由于少使用有机溶剂,利用分子中亲水性聚醚基及阴离子羧酸盐提供自乳化性,因此无毒,具有高效环保的特性。
具体实施方式
一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂及其制备方法,所述方法包括以下步骤:
(1)端羟基超支化纳米杂化聚合物(HB-SiO2)的合成:室温下在超声波分散仪中将纳米SiO2均匀分散于丙酮中,然后将氨基硅烷偶联剂加入分散液中,继续超声分散均匀,然后将分散液转移至三口烧瓶,在60~80℃下加热搅拌反应10~20h,然后加入AB2单体N,N-二羟乙基-3-胺基-丙酸甲酯反应2~3h,制得端羟基超支化纳米杂化聚合物HB-SiO2;
(2)NCO封端的聚氨酯预聚体(PU)的合成:将聚酯或聚醚多元醇和异氟尔酮二异氰酸酯以1:1.1~1.5的摩尔比混合,加混合物质量0.1~1.5%的二月桂酸二丁基锡做催化剂,在N2保护下,升温至60~90℃,持续搅拌反应1~2h后,加羧酸型扩链剂进行扩链,同时加入丙酮,在50~70℃下保温反应2~4h,制得NCO封端的聚氨酯预聚体PU;
(3)端氟烷基超支化纳米杂化聚氨酯(HBPUF-SiO2)的合成:在温度为60~80℃的条件下,将有机氟醇滴入步骤(2)所得PU的三口烧瓶内,搅拌反应3~5h;再将步骤(1)所得的HB-SiO2按一定比例(HB-SiO2中羟基与PU中NCO的摩尔比为1:2)加入上述反应体系,在60~80℃的条件下,持续反应3~5h至反应完全;
(4)HBPUF-SiO2乳液的制备:将步骤(3)的体系温度降至40~50℃,加有机胺中和并加水高速搅拌分散,然后在20~50℃下旋蒸半小时除去溶剂,制得固含量为30~50%的端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂。
步骤(1)中的氨基硅烷偶联剂为氨丙基三甲氧基硅烷或氨丙基三乙氧基硅烷。
步骤(1)中的超支化纳米杂化聚合物为端羟基超支化纳米杂化聚合物。
步骤(2)中的聚酯或聚醚多元醇为聚己二酸丁二醇酯、聚乙二醇中的一种。
步骤(2)中的羧酸型扩链剂为2,2-二羟甲基丙酸或2,2-二羟甲基丁酸。
步骤(3)中的有机氟醇为单官能团,选自全氟烷基乙醇[CF3(CF2)nCH2CH2OH](0≤n≤6)中的一种,用于超支化聚氨酯末端接枝。
步骤(4)中的有机胺为三乙胺或二乙胺,其用量与羧酸型扩链剂的物质的量相等。
步骤(1)中合成纳米杂化超支化聚合物的反应方程式如下:
步骤(2)中合成NCO封端的聚氨酯预聚体(PU)的反应方程式如下:
R1:R2:聚酯或聚醚链段
PU预聚体:
步骤(3)(4)合成HBPUF的反应方程式如下:
下面结合实施例来进一步说明本发明。
下述实施例中的试剂在使用前均需进行干燥处理,排除水分对反应的影响,所用的聚己二酸丁二醇酯的相对分子质量为1000,聚乙二醇的相对分子质量为1000。所用的二月桂酸二丁基锡作催化剂。
实施例一:
准确称取3.00g纳米SiO2分散于丙酮中,室温下在超声波分散仪中均匀分散;然后称取0.55g KH-550加入分散液中,继续超声分散均匀,再转移至三口烧瓶中,在60℃下搅拌反应15h,称取0.96g N,N-二羟乙基-3-胺基-丙酸甲酯加入上述体系,继续保温反应3h,80℃下烘干除去溶剂后即制得端羟基超支化纳米杂化聚合物HB-SiO2,备用。准确称取11.11g异氟尔酮二异氰酸酯(IPDI)和25.50g聚己二酸丁二醇酯(CMA-1044)加入三口烧瓶中,在N2保护下搅拌反应,待体系温度达到80℃,加两滴二月桂酸二丁基锡(DBTDL),继续反应1h后,降温,待温度降至60℃,加1.93g的2,2-二羟甲基丙酸(DMPA)扩链,同时加入10ml丙酮降低体系黏度,持续反应2.5h后得NCO封端的聚氨酯预聚体PU;升温,待体系温度达到80℃,再称取3.64g全氟己基乙醇,1h内滴加至反应体系,持续搅拌反应4h;把上述制备的HB-SiO2加入到反应体系,持续搅拌反应3h,降温,当温度降至40℃,加1.47g三乙胺中和,中和反应持续0.5h,最后称取110g去离子水边搅拌边滴加进行乳化,将制备的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得固含量为30%的端氟烷基超支化纳米杂化聚氨酯HBPUF-SiO2。
实施例二:
准确称取3.10g纳米SiO2分散于丙酮中,室温下在超声波分散仪中均匀分散;然后称取0.45g氨丙基三甲氧基硅烷加入分散液中,继续超声分散均匀,再转移至三口烧瓶中,在60℃下搅拌反应15h,称取0.96g N,N-二羟乙基-3-胺基-丙酸甲酯加入上述体系,继续保温反应3h。80℃下烘干除去溶剂后即制得端羟基超支化纳米杂化聚合物HB-SiO2,备用。准确称取13.34g异佛尔酮二异氰酸酯(IPDI)和33.40g聚乙二醇加入三口烧瓶中,在N2保护下搅拌反应,待体系温度达到80℃,加两滴二月桂酸二丁基锡(DBTDL),继续反应1h后得NCO封端的聚氨酯预聚体PU,降温,待温度降至60℃,加2.46g的2,2-二羟甲基丁酸(DMBA)扩链,同时加入20ml丙酮降低体系黏度,持续反应3h后;升温,待体系温度达到80℃,再称取3.64g全氟己基乙醇,1h内滴加至反应体系,持续搅拌反应4h;把上述制备的HB-SiO2加入到反应体系,持续搅拌反应4h,降温,当温度降至40℃,加1.21g二乙胺中和,中和反应持续0.5h,最后称取110g去离子水边搅拌边滴加进行乳化,将制备的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得固含量为35%的端氟烷基超支化纳米杂化聚氨酯HBPUF-SiO2。
实施例三:
准确称取5.80g纳米SiO2分散于丙酮中,室温下在超声波分散仪中均匀分散;然后称取1.11g KH-550加入分散液中,继续超声分散均匀,再转移至三口烧瓶中,在60℃下搅拌反应15h,称取1.91g N,N-二羟乙基-3-胺基-丙酸甲酯加入上述体系,继续保温反应3h。80℃下烘干除去溶剂后即制得端羟基超支化纳米杂化聚合物HB-SiO2,备用。准确称取17.78g异佛尔酮二异氰酸酯(IPDI)和38.00g聚己二酸丁二醇酯(CMA-1044)加入三口烧瓶中,在N2保护下搅拌反应,待体系温度达到80℃,加两滴二月桂酸二丁基锡(DBTDL),继续反应1h后,降温,待温度降至60℃,加2.93g的2,2-二羟甲基丙酸(DMPA)扩链,同时加入20ml丙酮降低体系黏度,持续反应3h后得NCO封端的聚氨酯预聚体PU;升温,待体系温度达到80℃,再称取7.28g全氟己基乙醇,2h内滴加至反应体系,持续搅拌反应4h;把上述制备的HB-SiO2加入到反应体系,持续搅拌反应3h,降温,当温度降至40℃,加2.23g三乙胺中和,中和反应持续0.5h,最后称取95g去离子水边搅拌边滴加进行乳化,将制备的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得固含量为45%的端氟烷基超支化纳米杂化聚氨酯HBPUF-SiO2。
实施例四:
准确称取5.50g纳米SiO2分散于丙酮中,室温下在超声波分散仪中均匀分散;然后称取0.55g KH-550加入分散液中,继续超声分散均匀,再转移至三口烧瓶中,在60℃下搅拌反应15h,称取0.96g N,N-二羟乙基-3-胺基-丙酸甲酯加入上述体系,继续保温反应3h。80℃下烘干除去溶剂后即制得端羟基超支化纳米杂化聚合物HB-SiO2,备用。准确称取11.11g异佛尔酮二异氰酸酯(IPDI)和20.00g聚己二酸丁二醇酯(CMA-1044)加入三口烧瓶中,在N2保护下搅拌反应,待体系温度达到80℃,加两滴二月桂酸二丁基锡(DBTDL),继续反应1h后,降温,待温度降至60℃,加2.66g的2,2-二羟甲基丙酸(DMPA)扩链,同时加入10ml丙酮降低体系黏度,持续反应2.5h后得NCO封端的聚氨酯预聚体PU;升温,待体系温度达到80℃,再称取3.64g全氟己基乙醇,1h内滴加至反应体系,持续搅拌反应4h;把上述制备的HB-SiO2加入到反应体系,持续搅拌反应3h,降温,当温度降至40℃,加2.02g三乙胺中和,中和反应持续0.5h,最后称取70g去离子水边搅拌边滴加进行乳化,将制备的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得固含量为40%的端氟烷基超支化纳米杂化聚氨酯HBPUF-SiO2。
通过数据比对,可以发现实施例一为最佳实施例。
Claims (7)
1.一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于:所述方法包括以下步骤:
(1)端羟基超支化纳米杂化聚合物的合成:室温下在超声波分散仪中将纳米SiO2均匀分散于丙酮中,然后将氨基硅烷偶联剂加入分散液中,继续超声分散均匀,然后将分散液转移至三口烧瓶,在60~80℃下加热搅拌反应10~20h,然后加入AB2单体N,N-二羟乙基-3-胺基-丙酸甲酯反应2~3h,制得端羟基超支化纳米杂化聚合物;
(2)NCO封端的聚氨酯预聚体的合成:将聚酯或聚醚多元醇和异氟尔酮二异氰酸酯以1:1.1~1.5的摩尔比混合,加混合物质量0.1~1.5%的二月桂酸二丁基锡做催化剂,在N2保护下,升温至60~90℃,持续搅拌反应1~2h后,加羧酸型扩链剂进行扩链,同时加入丙酮,在50~70℃下保温反应2~4h,制得NCO封端的聚氨酯预聚体PU;
(3)端氟烷基超支化纳米杂化聚氨酯的合成:在温度为60~80℃的条件下,将有机氟醇滴入步骤(2)所得的NCO封端的聚氨酯预聚体的三口烧瓶内,搅拌反应3~5h;再将步骤(1)所得的端羟基超支化纳米杂化聚合物按摩尔比为1:2的比例加入上述反应体系,在60~80℃的条件下,持续反应3~5h至反应完全;
(4)端氟烷基超支化纳米杂化聚氨酯乳液的制备:将步骤(3)的体系温度降至40~50℃,加有机胺中和并加水高速搅拌分散,然后在20~50℃下旋蒸半小时除去溶剂,制得固含量为30~50%的端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂。
2.根据权利要求1所述的一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于步骤(1)中的氨基硅烷偶联剂为氨丙基三甲氧基硅烷或氨丙基三乙氧基硅烷。
3.根据权利要求1或2所述的一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于步骤(1)中的超支化纳米杂化聚合物为端羟基超支化纳米杂化聚合物。
4.根据权利要求3所述的一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于步骤(2)中的聚酯或聚醚多元醇为聚己二酸丁二醇酯、聚乙二醇中的一种。
5.根据权利要求4所述的一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于步骤(2)中的羧酸型扩链剂为2,2-二羟甲基丙酸或2,2-二羟甲基丁酸。
6.根据权利要求5所述的一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于步骤(3)中的有机氟醇为单官能团,选自全氟烷基乙醇[CF3(CF2)nCH2CH2OH](0≤n≤6)中的一种,用于超支化聚氨酯末端接枝。
7.根据权利要求6所述的一种端氟烷基超支化聚氨酯纳米杂化皮革涂饰剂的制备方法,其特征在于步骤(4)中的有机胺为三乙胺或二乙胺,其用量与羧酸型扩链剂的物质的量相等。
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