CN109679327B - 一种纳米有机硅复合聚氨酯防水乳液 - Google Patents
一种纳米有机硅复合聚氨酯防水乳液 Download PDFInfo
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Abstract
本发明公开了一种纳米有机硅复合聚氨酯防水乳液,其特征在于:由纳米有机硅乳液与水性聚氨酯乳液复合而成,以质量百分比计,纳米有机硅乳液为34‑47%、水性聚氨酯乳液53‑66%;所述的纳米有机硅乳液由乙烯基纳米SiO2溶胶、双端烯基有机硅单体、单乙烯基有机硅单体、乳化剂、水、引发剂经乳液聚合制成;所述的水性聚氨酯乳液由聚醚二元醇、二异氰酸酯、二羟甲基丙酸、二羟基硅烷单体、三乙胺、乙二胺、催化剂、有机溶剂、水反应制成。纺织品表面的疏水性可通过增加其粗超度或在表面修饰低表面能物质。以聚硅氧烷为低表面能材料,纳米二氧化硅构造粗糙度,结合水性聚氨酯,既实现了良好的拒水性能,又改善了有机硅的附着力。
Description
技术领域
本发明涉及一种防水乳液,以纳米有机硅乳液与聚氨酯乳液复合而成,属于纳米功能材料领域。
背景技术
聚氨酯是一种嵌段聚合物,一般由低聚物二元醇的柔性长链构成链段,由多异氰酸酯和扩链剂构成硬段,具有耐磨、柔韧性好、附着力强等优点,在纺织品领域应用广泛。因为环保的原因,水性聚氨酯逐步取代了溶剂型聚氨酯。水性聚氨酯的大分子链中含大量水溶性基团,在耐水性、力学性能等方面稍有不足。
本发明拟采用纳米有机硅乳液对进行水性聚氨酯改性,将Si-O-Si、Si-C引入乳液体系,降低表面能、提高热稳定性,改善聚氨酯的耐候性、耐水性及力学性能。
发明内容
本发明目的是提供一种纳米有机硅复合聚氨酯防水乳液,以纳米有机硅乳液与水性聚氨酯乳液共混复合,以提升水性聚氨酯相关性能。
为实现上述目的,本发明采用的技术方案如下。
一种纳米有机硅复合聚氨酯防水乳液,由纳米有机硅乳液与水性聚氨酯乳液复合而成,以质量百分比计,纳米有机硅乳液为34-47%、水性聚氨酯乳液53-66%;
所述的纳米有机硅乳液由乙烯基纳米SiO2溶胶、双端烯基有机硅单体(如式1所示)、单乙烯基有机硅单体(如式2所示)、乳化剂、水、引发剂经乳液聚合制成;
(H3C)3Si-O-CH2CH2NH-CH2CH=CH2 式2
所述的水性聚氨酯乳液由聚醚二元醇、二异氰酸酯、二羟甲基丙酸、二羟基硅烷单体(如式3所示)、三乙胺、乙二胺、催化剂、有机溶剂、水反应制成;
所述的乙烯基纳米SiO2溶胶,由乙烯基硅烷偶联剂、催化剂、水、乳化剂制成,方法如下:将6份硅烷偶联剂KH-570、1.4份十二烷基硫酸钠、1.8份AEO-7、0.8份PEG-400加入到100份水中,搅拌、分散,再于搅拌下加入2.5份氨水,持续搅拌反应4h,形成乙烯基纳米SiO2溶胶。
所述的纳米有机硅乳液,制备方法如下:
(1)向乳化器中加入250份水、18份乙烯基纳米SiO2溶胶、24份双端烯基有机硅单体、21份单乙烯基有机硅单体及2份AEO-9、2份AEO-7、4份十二烷基苯磺酸钠,持续搅拌乳化0.5h,成预乳化液;
(2)取一半预乳化液置于带有控温、搅拌和冷凝装置的反应器中,在80℃时加入0.2份引发剂与4份水的溶液,保温反应0.5h;
(3)将另一半预乳化液置于恒压滴液漏斗中,缓慢滴入反应体系中,同时滴加0.4份引发剂与10份水的溶液,约2小时滴完,控制温度80℃,再反应2小时,得纳米有机硅乳液;
所述的水性聚氨酯乳液,制备方法如下:
a、将180份聚醚二元醇(N220)加入带有搅拌器、冷凝器、N2保护和温度计的反应器中,在60℃、搅拌下,加入52份IPDI,升温至70℃反应1.5h;
b、加入溶于DMF的9.4份DMPA,0.28份二月桂酸二丁基锡,在75℃搅拌反应0.5h;
c、降温至55℃,缓慢加入7份二羟基硅烷单体(如式3所示),反应至NCO达理论值,加剧烈搅拌下加入6份TEA,持续搅拌0.5h;
d、降温至25℃,加入384份去离子水,快速搅拌15min,再加入2.4份乙二胺,反应1.5h;
e、真空脱除丙酮,得水性聚氨酯乳液。
所述的引发剂为过硫酸钠、过硫酸钾、过硫酸铵中的一种。
有机硅在纺织品中广泛使用,赋予织物柔软、光滑手感,且有机硅表面能低,经其处理的织物可获得良好的疏水性。不过有机硅在织物表面的附着力弱、耐洗性差。
聚氨酯粘着力强,具有良好的韧性,通过共混,可实现有机硅聚氨酯两种材料的性能的互补。
聚氨酯分子链中含有强极性的氨基甲酸酯基、脲基,对织物具有强的粘结力,有机硅与聚氨酯的复合,在赋予织物良好拒水性的同时,提高了复合乳液成膜时与织物良好的粘结性能。在将乳液处理织物时,在织物表面成膜过程中,表面能低的有机硅链段向表面迁移,提供较好的拒水性;聚氨酯链段则通过其极性基团与织物形成氢键和化学键而产生强的粘结,进而达到优良的拒水性及粘结性能。
纺织品表面的疏水性可通过增加其表面的粗超度或在其表面修饰低表面能物质。本发明以聚硅氧烷为低表面能材料,纳米二氧化硅(SiO2)构造粗糙度,结合水性聚氨酯,既实现了良好的拒水性能,又改善了有机硅的附着力。
参与乳液聚合并用于改善乳液性能的含硅单体多为乙烯基硅氧烷偶联剂,由于含有可水解基团Si-O-C,在乳液聚合过程中,这些基团会发生一定程度的水解、缩合,从而使聚合物分子间过度交联而导致聚合反应失稳。尽管在聚合过程中,采用延迟滴加、添加水解抑制剂,仍难以获得有效的改性效果。本发明采用了Si(CH3)3基团的有机硅改性单体,由于其空间位阻大、不水解,大大提高了乳液聚合的稳定性,增加了聚合物中硅的含量,并使有机硅在聚合物分子链中的分布更均衡,有效增强聚合物的拒水性能。
具体实施方式
本发明所述物质单位“份”是指“质量份”。
本发明所涉双端烯基有机硅单体、单乙烯基有机硅单体、二羟基有机硅单体的制备方法如下。
双端烯基有机硅单体的制备方法:
在装有温度计、搅拌器的干燥四口烧瓶中,加入一定量的1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷和八甲基环四硅氧烷,边搅拌边升温至反应温度,并加入一定量的三氟甲基磺酸,保温反应一定时间。反应结束后加入无水Na2CO3搅拌中和至pH为6-7,过滤并将产物进行减压蒸馏(90℃,真空度-0.1Mpa以下),脱除未反应单体,得无色透明的液体产物。所涉反应过程如(1)所示。
单乙烯基有机硅单体由2-(三甲基硅氧基)乙醇胺与烯丙基氯反应制成,制备方法为:
在250mL三口瓶中,依次加入1mol 2-(三甲基硅氧基)乙醇胺、1.5mol三乙胺和100mL二氯甲烷。将三口瓶放置于冰水浴中,在此温度下缓慢滴加1.2mol烯丙基氯,滴加完毕后将反应体系升温至室温,并在此温度下继续反应1.5小时,停止反应,过滤除去三乙胺氯酸盐后,减压蒸馏除去二氯甲烷和过量的三乙胺,并收集的馏分,得乙烯基有机硅单体,N-2(三甲基硅氧基)乙基烯胺。所涉反应过程如(2)所示。
其中,2-(三甲基硅氧基)乙醇胺的制备方法为:在带有机械搅拌、温度计的反应器中,投入乙醇胺,搅拌滴加六甲基二硅氮烷,于5~50℃反应0.5~2h,反应完毕,经减压抽滤得2-(三甲基硅氧基)乙醇胺。乙醇胺与六甲基二硅氮烷的摩尔比为2:1。
所述的二羟基有机硅单体由二乙醇胺、NaOH、三甲基氯硅烷反应制得,制备方法如下:
将二乙醇胺和0.4mol/L的NaOH水溶液加入到带有搅拌器、回流冷凝管的三口烧瓶中,然后向烧瓶中缓慢加入三甲基氯硅烷,加料完毕后,在70℃下反应80min,减压蒸馏,除去多余的水及未反应的二乙醇胺,得到N-二乙醇-三甲基硅(二羟基有机硅单体);其中,所加入的二乙醇胺和三甲基氯硅烷的摩尔比为1.1:1,三甲基氯硅烷与NaOH摩尔比为1:1。反应过程如(3)所示。
实施例1
一种纳米有机硅复合聚氨酯防水乳液,由纳米有机硅乳液与水性聚氨酯乳液复合而成,以质量百分比计,纳米有机硅乳液为34%、水性聚氨酯乳液66%;
所述的纳米有机硅乳液由乙烯基纳米SiO2溶胶、双端烯基有机硅单体(如式1所示)、单乙烯基有机硅单体(如式2所示)、乳化剂、水、引发剂经乳液聚合制成;
(H3C)3Si—O-CH2CH2NH-CH2CH=CH2 式2
所述的水性聚氨酯乳液由聚醚二元醇、二异氰酸酯、二羟甲基丙酸、二羟基硅烷单体(如式3所示)、三乙胺、乙二胺、催化剂、有机溶剂、水反应制成;
所述的乙烯基纳米SiO2溶胶,由乙烯基硅烷偶联剂、催化剂、水、乳化剂制成,方法如下:将6份硅烷偶联剂KH-570、1.4份十二烷基硫酸钠、1.8份AEO-7、0.8份PEG-400加入到100份水中,搅拌、分散,再于搅拌下加入2.5份氨水,持续搅拌反应4h,形成乙烯基纳米SiO2溶胶。
所述的纳米有机硅乳液,制备方法如下:
(1)向乳化器中加入250份水、18份乙烯基纳米SiO2溶胶、24份双端烯基有机硅单体、21份单乙烯基有机硅单体及2份AEO-9、2份AEO-7、4份十二烷基苯磺酸钠,持续搅拌乳化0.5h,成预乳化液;
(2)取一半预乳化液置于带有控温、搅拌和冷凝装置的反应器中,在80℃时加入0.2份引发剂与4份水的溶液,保温反应0.5h;
(3)将另一半预乳化液置于恒压滴液漏斗中,缓慢滴入反应体系中,同时滴加0.4份引发剂与10份水的溶液,约2小时滴完,控制温度80℃,再反应2小时,得纳米有机硅乳液;
所述的水性聚氨酯乳液,制备方法如下:
a、将180份聚醚二元醇(N220)加入带有搅拌器、冷凝器、N2保护和温度计的反应器中,在60℃、搅拌下,加入52份IPDI,升温至70℃反应1.5h;
b、加入溶于DMF的9.4份DMPA,0.28份二月桂酸二丁基锡,在75℃搅拌反应0.5h;
c、降温至55℃,缓慢加入7份二羟基硅烷单体(如式3所示),反应至NCO达理论值,加剧烈搅拌下加入6份TEA,持续搅拌0.5h;
d、降温至25℃,加入384份去离子水,快速搅拌15min,再加入2.4份乙二胺,反应1.5h;
e、真空脱除丙酮,得水性聚氨酯乳液。
所述的引发剂为过硫酸钠。
实施例2
一种纳米有机硅复合聚氨酯防水乳液,由纳米有机硅乳液与水性聚氨酯乳液复合而成,以质量百分比计,纳米有机硅乳液为41%、水性聚氨酯乳液59%;
所述的纳米有机硅乳液由乙烯基纳米SiO2溶胶、双端烯基有机硅单体(如式1所示)、单乙烯基有机硅单体(如式2所示)、乳化剂、水、引发剂经乳液聚合制成;
(H3C)3Si-O-CH2CH2NH-CH2CH=CH2 式2
所述的水性聚氨酯乳液由聚醚二元醇、二异氰酸酯、二羟甲基丙酸、二羟基硅烷单体(如式3所示)、三乙胺、乙二胺、催化剂、有机溶剂、水反应制成;
所述的乙烯基纳米SiO2溶胶,由乙烯基硅烷偶联剂、催化剂、水、乳化剂制成,方法如下:将6份硅烷偶联剂KH-570、1.4份十二烷基硫酸钠、1.8份AEO-7、0.8份PEG-400加入到100份水中,搅拌、分散,再于搅拌下加入2.5份氨水,持续搅拌反应4h,形成乙烯基纳米SiO2溶胶。
所述的纳米有机硅乳液,制备方法如下:
(1)向乳化器中加入250份水、18份乙烯基纳米SiO2溶胶、24份双端烯基有机硅单体、21份单乙烯基有机硅单体及2份AEO-9、2份AEO-7、4份十二烷基苯磺酸钠,持续搅拌乳化0.5h,成预乳化液;
(2)取一半预乳化液置于带有控温、搅拌和冷凝装置的反应器中,在80℃时加入0.2份引发剂与4份水的溶液,保温反应0.5h;
(3)将另一半预乳化液置于恒压滴液漏斗中,缓慢滴入反应体系中,同时滴加0.4份引发剂与10份水的溶液,约2小时滴完,控制温度80℃,再反应2小时,得纳米有机硅乳液;
所述的水性聚氨酯乳液,制备方法如下:
a、将180份聚醚二元醇(N220)加入带有搅拌器、冷凝器、N2保护和温度计的反应器中,在60℃、搅拌下,加入52份IPDI,升温至70℃反应1.5h;
b、加入溶于DMF的9.4份DMPA,0.28份二月桂酸二丁基锡,在75℃搅拌反应0.5h;
c、降温至55℃,缓慢加入7份二羟基硅烷单体(如式3所示),反应至NCO达理论值,加剧烈搅拌下加入6份TEA,持续搅拌0.5h;
d、降温至25℃,加入384份去离子水,快速搅拌15min,再加入2.4份乙二胺,反应1.5h;
e、真空脱除丙酮,得水性聚氨酯乳液。
所述的引发剂为过硫酸钾。
实施例3
一种纳米有机硅复合聚氨酯防水乳液,由纳米有机硅乳液与水性聚氨酯乳液复合而成,以质量百分比计,纳米有机硅乳液为47%、水性聚氨酯乳液53%;
所述的纳米有机硅乳液由乙烯基纳米SiO2溶胶、双端烯基有机硅单体(如式1所示)、单乙烯基有机硅单体(如式2所示)、乳化剂、水、引发剂经乳液聚合制成;
(H3C)3Si-O-CH2CH2NH-CH2CH=CH2 式2
所述的水性聚氨酯乳液由聚醚二元醇、二异氰酸酯、二羟甲基丙酸、二羟基硅烷单体(如式3所示)、三乙胺、乙二胺、催化剂、有机溶剂、水反应制成;
所述的乙烯基纳米SiO2溶胶,由乙烯基硅烷偶联剂、催化剂、水、乳化剂制成,方法如下:将6份硅烷偶联剂KH-570、1.4份十二烷基硫酸钠、1.8份AEO-7、0.8份PEG-400加入到100份水中,搅拌、分散,再于搅拌下加入2.5份氨水,持续搅拌反应4h,形成乙烯基纳米SiO2溶胶。
所述的纳米有机硅乳液,制备方法如下:
(1)向乳化器中加入250份水、18份乙烯基纳米SiO2溶胶、24份双端烯基有机硅单体、21份单乙烯基有机硅单体及2份AEO-9、2份AEO-7、4份十二烷基苯磺酸钠,持续搅拌乳化0.5h,成预乳化液;
(2)取一半预乳化液置于带有控温、搅拌和冷凝装置的反应器中,在80℃时加入0.2份引发剂与4份水的溶液,保温反应0.5h;
(3)将另一半预乳化液置于恒压滴液漏斗中,缓慢滴入反应体系中,同时滴加0.4份引发剂与10份水的溶液,约2小时滴完,控制温度80℃,再反应2小时,得纳米有机硅乳液;
所述的水性聚氨酯乳液,制备方法如下:
a、将180份聚醚二元醇(N220)加入带有搅拌器、冷凝器、N2保护和温度计的反应器中,在60℃、搅拌下,加入52份IPDI,升温至70℃反应1.5h;
b、加入溶于DMF的9.4份DMPA,0.28份二月桂酸二丁基锡,在75℃搅拌反应0.5h;
c、降温至55℃,缓慢加入7份二羟基硅烷单体(如式3所示),反应至NCO达理论值,加剧烈搅拌下加入6份TEA,持续搅拌0.5h;
d、降温至25℃,加入384份去离子水,快速搅拌15min,再加入2.4份乙二胺,反应1.5h;
e、真空脱除丙酮,得水性聚氨酯乳液。
所述的引发剂为过硫酸铵。
上述3个实施例纳米有机硅复合聚氨酯防水乳液,外观呈淡蓝色半透明状,经3000r/min离心1h,未分层、也未见沉淀。(参照<GB/T11175-2002合成树脂乳液试验方法>方法测试)
将上述3个实施例的纳米有机硅复合聚氨酯防水乳液用于涤纶面料的防水整理,处方为:纳米有机硅复合聚氨酯防水乳液20份、增稠剂2份、水78份;工艺为:涂层→预烘(90℃、3min)→焙烘(160℃、90s),涤纶面料成分及规格为100%涤纶、150D*150D。参照GB/T4745-2012、GB/T4744-2013方法,对涂层后的涤纶面料进行了耐水性、拒水性能测试,结果如表1所示。
表1涤纶涂层试样耐水、防水性能
试样 | 拒水性/级 | 拒水性/级(洗后) | 防水性(静水压)/KPa |
实施例1 | 4 | 3 | 47.3 |
实施例2 | 5 | 4 | 51.6 |
实施例3 | 5 | 4 | 54.2 |
涤纶面料经实施例的纳米有机硅复合聚氨酯防水乳液涂层整理后,拒水等级4级以上,静水压47KPa以上,防水、拒水性能优异。
Claims (4)
1.一种纳米有机硅复合聚氨酯防水乳液,其特征在于:由纳米有机硅乳液与水性聚氨酯乳液复合而成,以质量百分比计,纳米有机硅乳液为34-47%、水性聚氨酯乳液53-66%;
所述的纳米有机硅乳液由乙烯基纳米SiO2溶胶、如式1所示的双端烯基有机硅单体、如式2所示的单乙烯基有机硅单体、乳化剂、水、引发剂经乳液聚合制成;
(H3C)3Si-O-CH2CH2NH-CH2CH=CH2 式2
所述的水性聚氨酯乳液由聚醚二元醇、二异氰酸酯、二羟甲基丙酸、如式3所示的二羟基硅烷单体、三乙胺、乙二胺、催化剂、有机溶剂、水反应制成;
所述的乙烯基纳米SiO2溶胶,由乙烯基硅烷偶联剂、催化剂、水、乳化剂制成,方法如下:将6份硅烷偶联剂KH-570、1.4份十二烷基硫酸钠、1.8份AEO-7、0.8份PEG-400加入到100份水中,搅拌、分散,再于搅拌下加入2.5份氨水,持续搅拌反应4h,形成乙烯基纳米SiO2溶胶;
所述双端烯基有机硅单体的制备方法:
在装有温度计、搅拌器的干燥四口烧瓶中,加入一定量的1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷和八甲基环四硅氧烷,边搅拌边升温至反应温度,并加入一定量的三氟甲基磺酸,保温反应一定时间,反应结束后加入无水Na2CO3搅拌中和至pH为6-7,过滤并将产物90℃、真空度-0.1Mpa以下进行减压蒸馏,脱除未反应单体,得无色透明的液体产物,所涉反应过程如(1)所示;
所述单乙烯基有机硅单体由2-(三甲基硅氧基)乙醇胺与烯丙基氯反应制成,制备方法为:
在250mL三口瓶中,依次加入1mol 2-(三甲基硅氧基)乙醇胺、1.5mol三乙胺和100mL二氯甲烷,将三口瓶放置于冰水浴中,在此温度下缓慢滴加1.2mol烯丙基氯,滴加完毕后将反应体系升温至室温,并在此温度下继续反应1.5小时,停止反应,过滤除去三乙胺氯酸盐后,减压蒸馏除去二氯甲烷和过量的三乙胺,并收集馏分,得乙烯基有机硅单体,N-2(三甲基硅氧基)乙基烯胺,所涉反应过程如(2)所示;
其中,2-(三甲基硅氧基)乙醇胺的制备方法为:在带有机械搅拌、温度计的反应器中,投入乙醇胺,搅拌滴加六甲基二硅氮烷,于5~50℃反应0.5~2h,反应完毕,经减压抽滤得2-(三甲基硅氧基)乙醇胺,乙醇胺与六甲基二硅氮烷的摩尔比为2:1;
所述的二羟基硅烷单体由二乙醇胺、NaOH、三甲基氯硅烷反应制得,制备方法如下:
将二乙醇胺和0.4mol/L的NaOH水溶液加入到带有搅拌器、回流冷凝管的三口烧瓶中,然后向烧瓶中缓慢加入三甲基氯硅烷,加料完毕后,在70℃下反应80min,减压蒸馏,除去多余的水及未反应的二乙醇胺,得到N-二乙醇-三甲基硅,即二羟基硅烷单体;其中,所加入的二乙醇胺和三甲基氯硅烷的摩尔比为1.1:1,三甲基氯硅烷与NaOH摩尔比为1:1,反应过程如(3)所示
2.根据权利要求1所述的一种纳米有机硅复合聚氨酯防水乳液,其特征在于:所述的纳米有机硅乳液,制备方法如下:
(1)向乳化器中加入250份水、18份乙烯基纳米SiO2溶胶、24份双端烯基有机硅单体、21份单乙烯基有机硅单体及2份AEO-9、2份AEO-7、4份十二烷基苯磺酸钠,持续搅拌乳化0.5h,成预乳化液;
(2)取一半预乳化液置于带有控温、搅拌和冷凝装置的反应器中,在80℃时加入0.2份引发剂与4份水的溶液,保温反应0.5h;
(3)将另一半预乳化液置于恒压滴液漏斗中,缓慢滴入反应体系中,同时滴加0.4份引发剂与10份水的溶液,2小时滴完,控制温度80℃,再反应2小时,得纳米有机硅乳液。
3.根据权利要求1所述的一种纳米有机硅复合聚氨酯防水乳液,其特征在于:所述的水性聚氨酯乳液,制备方法如下:
a、将180份聚醚二元醇N220加入带有搅拌器、冷凝器、N2保护和温度计的反应器中,在60℃、搅拌下,加入52份IPDI,升温至70℃反应1.5h;
b、加入溶于DMF的9.4份DMPA,0.28份二月桂酸二丁基锡,在75℃搅拌反应0.5h;
c、降温至55℃,缓慢加入7份如式3所示的二羟基硅烷单体,反应至NCO达理论值,加剧烈搅拌下加入6份TEA,持续搅拌0.5h;
d、降温至25℃,加入384份去离子水,快速搅拌15min,再加入2.4份乙二胺,反应1.5h;
e、真空脱除丙酮,得水性聚氨酯乳液。
4.根据权利要求1-3任一所述的一种纳米有机硅复合聚氨酯防水乳液,其特征在于:所述的引发剂为过硫酸钠、过硫酸钾、过硫酸铵中的一种。
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CN105646799A (zh) * | 2016-01-13 | 2016-06-08 | 广州中国科学院工业技术研究院 | 阳离子型含硅丙烯酸酯织物拒水剂及其制备方法 |
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