CN111270525A - 一种阻燃防污功能水性聚氨酯织物整理剂及其制备方法 - Google Patents
一种阻燃防污功能水性聚氨酯织物整理剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种阻燃防污功能水性聚氨酯织物整理剂的制备方法,包括以下步骤:1)DEHPA改性聚氨酯预聚体的合成:过量的异佛尔酮二异氰酸酯与聚酯多元醇或聚醚多元醇、2,2‑二羟甲基丙酸、N,N‑双(2‑羟乙基)磷酸二乙酯反应得到含异氰酸酯基的DEHPA改性聚氨酯预聚体;2)有机氟末端改性聚氨酯的合成:令有机氟醇与过量的含异氰酸酯基的DEHPA改性聚氨酯预聚体反应,得到有机氟末端改性聚氨酯;3)阻燃防污功能水性聚氨酯的合成:令有机氟末端改性聚氨酯与交联剂反应,得到阻燃防污功能水性聚氨酯。所制备的阻燃防污功能水性聚氨酯乳液可用于织物的整理,可简便地处理织物并赋予其良好的阻燃防污功能。
Description
技术领域
本发明属于改性聚氨酯材料领域,具体涉及一种阻燃防污功能水性聚氨酯织物整理剂的制备方法。
背景技术
聚氨酯(PU)材料具有耐磨、耐化学药品、柔韧性好、粘合强度大、高强度以及抗撕裂等优良性能,被广泛用作涂料、弹性体、皮革、织物整理剂、粘接剂等领域。溶剂型聚氨酯,由于有机溶剂含量大,挥发性有机化合物(VOC)的排放量大,且有毒、易燃,严重污染环境,故水性聚氨酯成为近年来主要的发展方向。水性聚氨酯是以水作为分散介质,具有低VOC含量、无毒、安全性高、不污染环境、节省能源等优点,获得了越来越广泛的应用。但其成膜材料热稳定性低、耐水性差,且具有可燃性。因此,同时改善水性聚氨酯材料的疏水和阻燃性能具有重要意义。
众所周知,氟原子具有半径小、电负性大、强电子亲和性、极高的电解能,将含氟基团引入WPU中,能使WPU具有低表面能、耐热性、抗沾污性、良好的憎水憎油性能和化学稳定性等,广泛应用于诸多领域。
阻燃改性聚氨酯通常包括物理添加阻燃剂和化学键入反应型阻燃剂两种改性方法。前者由于添加量大,存在与聚合物基质不相容等从而影响聚合物的热、力学性能等问题,而后者由于阻燃剂化学键入聚氨酯分子链中,分布均匀且与聚合物基质相容性好,因此,聚合物的综合应用性能佳,近年来已逐渐成为了阻燃改性聚氨酯的首先方法。从环境安全的角度及阻燃效果来看,反应性含磷类阻燃剂逐渐得到研究人员和市场的认可。其制备方法多利用含磷基活性中心,如三氯氧磷(POCl3)、苯基/烷基二(一)氯氧磷、磷酸、亚磷酸、磷化氢等与活性羟基化合物、氨基化合物等反应以制备含双羟基(胺基)磷类阻燃剂或多羟基(胺基)磷类阻燃剂,再通过其与异氰酸酯间的反应从而引入到聚氨酯分子链中制得阻燃改性聚氨酯。如Patel等先通过双酚-A、癸二酸、聚乙二醇(PEG-600)与三氯氧磷间的反应制备了一种含羧基的聚酯型含磷阻燃剂,然后与异氰酸酯进行聚加成反应后经中和加水乳化制得了一种阻燃水性聚氨酯乳液[Progress in Organic Coatings,2018,125,186-194.]。Wazarkar等通过N-甲基乙醇胺与三氯氧磷反应制得了含磷三元醇(FROH),然后与异佛尔酮二异氰酸酯、聚乙二醇、二羟甲基丙酸进行聚加成反应,经中和乳化后制得了系列阻燃水性聚氨酯分散液[Progress in Organic Coatings,2015,87,75-82.]。Bhoyate等用苯基亚磷酸和环氧丙烷反应制备了一种含磷基的扩链剂并用于制备刚性聚氨酯泡沫,结果1.5wt%的磷即可使聚氨酯获得很好的阻燃性能[Journal of Applied Polymer Science,2018,DOI:10.1002/APP.46224]。Rao等用苯基二氯氧磷与乙二醇反应制得一种含磷基聚多醇PDEO,然后PDEO再与甲苯二异氰酸酯、聚多醇、二羟甲基丙酸等进行聚加成反应制得了系列阻燃聚氨酯乳液[Polymer Degradation and Stability,2018,153,192-200]。而磷氮反应型阻燃剂具有协同阻燃功效,不仅效率高,对PU性能的影响也小,且低毒、少烟、环保、符合国家环保要求,是一类较为理想的阻燃剂。
发明内容
为克服上述技术的不足,本发明的目的是提供一种阻燃防污功能水性聚氨酯织物整理剂的制备方法,将其应用于织物的整理,可简便地赋予织物高效阻燃和防污功能。
本发明采用的技术方案为:一种阻燃防污功能水性聚氨酯织物整理剂的制备方法,其特征在于:
包括以下步骤:
1)磷氮型阻燃剂的合成:在冰水浴中,向含有亚磷酸二乙酯、四氢呋喃和四氯化碳的混合溶液中逐滴滴加含有二乙醇胺、三乙胺和四氢呋喃的混合液体,滴加完毕后,在室温条件下反应10h,过滤并取滤液在40℃和-0.1MPa的条件下旋蒸去除溶剂,制得淡黄色透明液体,即N,N-双(2-羟乙基)磷酸二乙酯阻燃剂(DEHPA)。
2)DEHPA改性聚氨酯预聚体的合成:以异佛尔酮二异氰酸酯、聚酯多元醇或聚醚多元醇为原料,二月桂酸二丁基锡为催化剂,在80℃下反应1小时,然后加入2,2-二羟甲基丙酸扩链,反应1h,降温至65℃,逐滴加入上述1)体系中制备的磷氮型阻燃剂,滴加完毕后升温至80℃,反应3小时,期间加入丙酮作为溶剂降低粘度,制得磷氮型阻燃改性聚氨酯预聚体;
3)有机氟末端改性聚氨酯的合成:在温度为80℃的条件下,将有机氟醇用适量丙酮溶解逐滴加入上述2)反应体系,加热搅拌1小时至反应完全,制得有机氟单侧封端的聚氨酯;
4)阻燃防污功能水性聚氨酯乳液的制备:将交联剂用适量丙酮溶解,逐滴加入上述3)反应体系,滴加完毕后,在80℃下反应1小时,制得交联型聚氨酯。体系降温至40℃,加入三乙胺中和半小时,然后加水高速搅拌分散,在50℃和-0.1MPa下旋蒸半小时去除溶剂,制得固含量为30%的阻燃防污功能水性聚氨酯乳液DEHPA-F-WPU。
步骤1)中,磷酸二乙酯、二乙醇胺和三乙胺的用量为0.1mol,溶剂四氢呋喃和四氯化碳的用量为40mL和10mL,溶剂四氢呋喃的用量为50mL。
步骤2)中,聚酯多元醇或聚醚多元醇为聚己内酯二醇、聚四氢呋喃二醇中的一种。异佛尔酮二异氰酸酯的用量为54mmol,聚酯多元醇或聚醚多元醇的用量为10.8mmol,二月桂酸二丁基锡为0.1ml,2,2-二羟甲基丙酸的用量为12.8mmol,DEHPA的用量为25.5mmol,溶剂的用量为10mL。
步骤3)中的有机氟醇为全氟己基乙醇、全氟-1-辛醇中的一种,且均为单官能团的有机氟,用于聚氨酯预聚体单侧封端。有机氟醇的用量为4.9mmol,溶剂的用量为10mL。
步骤4)中的交联剂为三羟甲基丙烷、三乙醇胺或季戊四醇中的一种。三羟甲基丙烷和三乙醇胺的用量为1.63mmol,季戊四醇的用量为1.23mmol,溶剂的用量为10mL。
步骤4)中,三乙胺的用量为1.23mmol。
与现有技术相比,本发明具有如下优点和效果:
本发明利用亚磷酸二乙酯和二乙醇胺间的反应简便地制得具有磷氮反应型阻燃剂,通过聚加成反应引入聚氨酯预聚体后,采用有机氟烷基一元醇单侧封端,再利用交联剂交联,经中和乳化后制得具有阻燃防污功能的聚氨酯乳液,将其用于织物整理,可简便赋予织物高效阻燃和防污功能。
附图说明
图1为DEHPA合成路线示意图;
图2为磷氮型阻燃剂改性聚氨酯预聚体的合成路线示意图;
图3为DEHPA-F-WPU的合成路线示意图。
具体实施方式
下面结合具体实施方式对本发明进行详细地说明。
一种阻燃防污功能水性聚氨酯织物整理剂的制备方法,具体由以下步骤实现:
1)磷氮型阻燃剂的合成:在冰水浴中,向含有0.1mol的亚磷酸二乙酯、40mL的四氢呋喃和10mL的四氯化碳的混合溶液中逐滴滴加含有0.1mol的二乙醇胺、0.1mol的三乙胺和50mL的四氢呋喃的混合液体,滴加完毕后,在室温条件下反应10h,过滤并取滤液在40℃和-0.1MPa的条件下旋蒸去除溶剂,制得淡黄色透明液体,即N,N-双(2-羟乙基)磷酸二乙酯阻燃剂(DEHPA)。
2)DEHPA改性聚氨酯预聚体的合成:以54mmol的异佛尔酮二异氰酸酯和10.8mmol的聚酯多元醇或聚醚多元醇为原料,0.1mL的二月桂酸二丁基锡为催化剂,在80℃下反应1小时,然后加入12.8mmol的2,2-二羟甲基丙酸扩链,反应1h,降温至65℃,逐滴加入上述1)体系中制备的磷氮型阻燃剂,滴加完毕后升温至80℃,反应3小时,期间加入10mL的丙酮作为溶剂降低粘度,制得磷氮型阻燃改性聚氨酯预聚体;
3)有机氟末端改性聚氨酯的合成:在温度为80℃的条件下,将4.9mmol的有机氟醇用10mL丙酮溶解逐滴加入上述2)反应体系,加热搅拌1小时至反应完全,制得有机氟单侧封端的聚氨酯;
4)阻燃防污功能水性聚氨酯乳液的制备:将1.63mmol或1.23mmol的交联剂用10mL的丙酮溶解,逐滴加入上述3)反应体系,滴加完毕后,在80℃下反应1小时,制得交联型聚氨酯。体系降温至40℃,加入1.23mmol的三乙胺中和半小时,然后加水高速搅拌分散,在50℃和-0.1MPa下旋蒸半小时去除溶剂,制得固含量为30%的阻燃防污功能水性聚氨酯乳液DEHPA-F-WPU。
步骤2)中,聚酯多元醇或聚醚多元醇为聚己内酯二醇、聚四氢呋喃二醇中的一种。
步骤3)中的有机氟醇为全氟己基乙醇、全氟-1-辛醇中的一种,且均为单官能团的有机氟,用于聚氨酯预聚体单侧封端。
步骤4)中的交联剂为三羟甲基丙烷、三乙醇胺或季戊四醇中的一种。
步骤1)中合成N,N-双(2-羟乙基)磷酸二乙酯阻燃剂的反应方程式如图1所示。
步骤2)中磷氮型阻燃剂改性聚氨酯预聚体的反应方程式如图2所示。
步骤(3)~(4)合成DEHPA-F-WPU的反应方程式如图3所示。
下面结合具体实施例以及对比例来进一步说明本发明:
实例中的试剂在使用前均需进行干燥处理,所用的聚己内酯二醇的相对分子质量为1000,聚四氢呋喃二醇的相对分子质量为1000,所用的二月桂酸二丁基锡(DBTDL)作催化剂。
实施例一:
准确称取13.8g(0.1mol)亚磷酸二乙酯,50mL四氢呋喃和10mL四氯化碳的于250mL三口烧瓶中,在冰水浴条件下,搅拌,待体系温度为0-5℃时,逐滴滴加溶有10.5g(0.1mol)二乙醇胺,10.11g(0.1mol)三乙胺和50mL四氢呋喃的混合液,滴加完毕后,在室温条件下反应10h,过滤,取液体,在40℃,-0.1MPa条件下旋蒸除溶剂,制得淡黄色透明液体,即N,N-双(2-羟乙基)磷酸二乙酯(DEHPA)。
准确称取12g(0.054mol)异佛尔酮二异氰酸酯(IPDI)和10.8g(0.0108mol)聚己内酯二醇(PCL1000),加入三口烧瓶中,油浴加热搅拌,待体系温度达到80℃时,加入二月桂酸二丁基锡(DBTDL)3滴,通冷凝水,继续反应1小时,加入1.72g(0.0128mol)2,2-二羟甲基丙酸(DMPA)扩链,同时加入10mL丙酮降黏,持续反应1h后开始降温至60℃,称取6.15g(0.0255mol)磷氮型阻燃剂,1h内滴加至反应体系,滴加完毕后升温至80℃,反应3小时,再称取1.78g(0.0049mol)全氟己基乙醇(S104)溶于10mL丙酮中,1h内滴加至反应体系,持续加热搅拌1h后,称取0.22g(0.00163mol)三羟甲基丙烷(TMP)溶于10mL丙酮中,1h内滴加至反应体系,持续加热搅拌0.5h后对体系降温,当温度降至40℃,加入1.3g(0.0128mol)三乙胺(TEA)进行中和,中和反应持续0.5h,最后称取77.74g去离子水边高速搅拌边滴加进行乳化,将制得的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得具有阻燃防污功能的水性聚氨酯乳液DEHPA-F-WPU-1。
实施例二:
准确称取13.8g(0.1mol)亚磷酸二乙酯,50mL四氢呋喃和10mL四氯化碳的于250mL三口烧瓶中,在冰水浴条件下,搅拌,待体系温度为0-5℃时,逐滴滴加溶有10.5g(0.1mol)二乙醇胺,10.11g(0.1mol)三乙胺和50mL四氢呋喃的混合液,滴加完毕后,在室温条件下反应10h,过滤,取液体,在40℃,-0.1MPa条件下旋蒸除溶剂,制得淡黄色透明液体,即N,N-双(2-羟乙基)磷酸二乙酯(DEHPA)。
准确称取12g(0.054mol)异佛尔酮二异氰酸酯(IPDI)和10.8g(0.0108mol)聚四氢呋喃二醇,加入三口烧瓶中,油浴加热搅拌,待体系温度达到80℃时,加入二月桂酸二丁基锡(DBTDL)3滴,通冷凝水,继续反应1小时,加入1.72g(0.0128mol)2,2-二羟甲基丙酸(DMPA)扩链,同时加入10mL丙酮降黏,持续反应1h后开始降温至60℃,称取6.15g(0.0255mol)磷氮型阻燃剂,1h内滴加至反应体系,滴加完毕后升温至80℃,反应3小时,再称取1.96g(0.0049mol)全氟-1-辛醇溶于10mL丙酮中,1h内滴加至反应体系,持续加热搅拌1h后,称取0.24g(0.00163mol)三乙醇胺溶于10mL丙酮中,1h内滴加至反应体系,持续加热搅拌0.5h后对体系降温,当温度降至40℃,加入1.3g(0.0128mol)三乙胺(TEA)进行中和,中和反应持续0.5h,最后称取79.73g去离子水边高速搅拌边滴加进行乳化,将制得的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得具有阻燃防污功能的水性聚氨酯乳液DEHPA-F-WPU-2。
实施例三:
准确称取13.8g(0.1mol)亚磷酸二乙酯,50mL四氢呋喃和10mL四氯化碳的于250mL三口烧瓶中,在冰水浴条件下,搅拌,待体系温度为0-5℃时,逐滴滴加溶有10.5g(0.1mol)二乙醇胺,10.11g(0.1mol)三乙胺和50mL四氢呋喃的混合液,滴加完毕后,在室温条件下反应10h,过滤,取液体,在40℃,-0.1MPa条件下旋蒸除溶剂,制得淡黄色透明液体,即N,N-双(2-羟乙基)磷酸二乙酯(DEHPA)。
准确称取12g(0.054mol)异佛尔酮二异氰酸酯(IPDI)和10.8g(0.0108mol)聚己内酯二醇(PCL1000),加入三口烧瓶中,油浴加热搅拌,待体系温度达到80℃时,加入二月桂酸二丁基锡(DBTDL)3滴,通冷凝水,继续反应1小时,加入1.72g(0.0128mol)2,2-二羟甲基丙酸(DMPA)扩链,同时加入10mL丙酮降黏,持续反应1h后开始降温至60℃,称取6.15g(0.0255mol)磷氮型阻燃剂,1h内滴加至反应体系,滴加完毕后升温至80℃,反应3小时,再称取1.78g(0.0049mol)全氟己基乙醇(S104)溶于10mL丙酮中,1h内滴加至反应体系,持续加热搅拌1h后,称取0.17g(0.00123mol)季戊四醇溶于10mL丙酮中,1h内滴加至反应体系,持续加热搅拌0.5h后对体系降温,当温度降至40℃,加入1.3g(0.0128mol)三乙胺(TEA)进行中和,中和反应持续0.5h,最后称取79.15g去离子水边高速搅拌边滴加进行乳化,将制得的乳液在50℃,-0.1MPa条件下旋蒸0.5h,除去有机溶剂,最终制得具有阻燃防污功能的水性聚氨酯乳液DEHPA-F-WPU-3。
对比例一:
参照实施例一,将实施例一中的DEHPA替换为等物质的量的其他含磷阻燃扩链剂PPA-PO,其结构如下:
其余制备原料、工艺与实施例一完全一致。然后,通过比较二种阻燃织物整理剂处理织物后的性能,发现对比例一产品的阻燃性能更好,其原因可能是实施例一中所用为磷氮反应型阻燃剂(DEHPA),它们具有协同阻燃功效,效率更高。
对比例二:
参照实施例二,采用不同加料顺序,尤其是交联剂加入过早来制备产品,制备过程中发现产品易出现交联过度从而产生凝胶缺陷,导致反应无法继续或产品存在严重缺陷。
对比例三:
参照实施例三,将实施例三中的有机氟醇缺省,所制备的织物整理剂与实施例三对比,发现实施例三中的有机氟醇不仅赋予产品良好的防污功能,还带来了阻燃性能的提升。这可能源自于有机氟的协同作用。
本发明的内容不限于实施例所列举,本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换,均为本发明的权利要求所涵盖。
Claims (9)
1.一种阻燃防污功能水性聚氨酯织物整理剂的制备方法,其特征在于,包括如下步骤:
1)DEHPA改性聚氨酯预聚体的合成:过量的异佛尔酮二异氰酸酯与聚酯多元醇或聚醚多元醇、2,2-二羟甲基丙酸、N,N-双(2-羟乙基)磷酸二乙酯反应得到含异氰酸酯基的DEHPA改性聚氨酯预聚体;
2)有机氟末端改性聚氨酯的合成:令有机氟醇与过量的含异氰酸酯基的DEHPA改性聚氨酯预聚体反应,得到有机氟末端改性聚氨酯;
3)阻燃防污功能水性聚氨酯的合成:令有机氟末端改性聚氨酯与交联剂反应,得到阻燃防污功能水性聚氨酯。
2.如权利要求1所述的方法,其特征在于,包括如下步骤:
1)异佛尔酮二异氰酸酯与聚酯多元醇或聚醚多元醇在80℃反应;加入2,2-二羟甲基丙酸继续反应;降温后缓慢加入N,N-双(2-羟乙基)磷酸二乙酯升温至80℃继续反应;反应过程中,加入适量非反应性溶剂降低体系粘度;
2)保持体系80℃,将含有机氟醇的溶液逐渐加入步骤1)体系,充分反应;
3)向步骤2)体系缓慢加入含交联剂的溶液,在80℃充分反应,得到阻燃防污功能水性聚氨酯。
3.如权利要求2所述的方法,其特征在于,聚酯多元醇或聚醚多元醇为聚己内酯二醇、聚四氢呋喃二醇中的一种;有机氟醇为全氟己基乙醇、全氟-1-辛醇中的一种;交联剂为三羟甲基丙烷、三乙醇胺或季戊四醇中的一种;非反应性溶剂、用于溶解有机氟醇的溶剂、用于溶解交联剂的溶剂均为丙酮。
4.如权利要求3所述的方法,其特征在于,步骤1)的含异氰酸酯基的DEHPA改性聚氨酯预聚体由包括如下原料的体系反应得到:异佛尔酮二异氰酸酯54mmol,聚酯多元醇或聚醚多元醇10.8mmol,二月桂酸二丁基锡0.1ml,2,2-二羟甲基丙酸12.8mmol,N,N-双(2-羟乙基)磷酸二乙酯25.5mmol,丙酮10mL;
步骤2)中含有机氟醇的溶液包括:有机氟醇4.9mmol,丙酮10mL;
步骤3)中含交联剂的溶液包括:丙酮10mL;当交联剂为三羟甲基丙烷或三乙醇胺时,其用量为1.63mmol:当交联剂为季戊四醇时,其用量为1.23mmol。
5.如权利要求2-4任一项所述的方法,其特征在于,反应完毕后,将体系降温,加入三乙胺中和,然后加水高速分散,去除溶剂,制得阻燃防污功能水性聚氨酯乳液DEHPA-F-WPU。
7.如权利要求6所述的方法,其特征在于,N,N-双(2-羟乙基)磷酸二乙酯由包括如下步骤的方法得到:
在冰水浴中,向含有亚磷酸二乙酯、四氢呋喃和四氯化碳的混合溶液中逐滴滴加含有二乙醇胺、三乙胺和四氢呋喃的混合液体,滴加完毕后,在室温条件下反应10h,过滤并取滤液在40℃和-0.1MPa的条件下旋蒸去除溶剂,制得淡黄色透明液体,即N,N-双(2-羟乙基)磷酸二乙酯阻燃剂DEHPA。
8.如权利要求7所述的方法,其特征在于,含有亚磷酸二乙酯、四氢呋喃和四氯化碳的混合溶液中含磷酸二乙酯0.1mol、四氢呋喃40mL、四氯化碳10mL;含有二乙醇胺、三乙胺和四氢呋喃的混合液体中含有二乙醇胺0.1mol、三乙胺0.1mol、四氢呋喃50mL。
9.权利要求1-8任一项所述方法制备阻燃防污功能水性聚氨酯织物整理剂。
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