CN112250819A - 一种聚氨酯基多功能互穿网络聚合物及其制备方法 - Google Patents
一种聚氨酯基多功能互穿网络聚合物及其制备方法 Download PDFInfo
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Abstract
本发明提供一种聚氨酯基多功能互穿网络聚合物及其制备方法,通过交联聚氨酯(Ⅰ)与多功能聚氨酯(Ⅱ)之间的大分子链间网络互穿和链扣,形成聚氨酯基互穿网络聚合物。其中多功能聚氨酯(Ⅱ)大分子主链上悬挂的聚乙二醇链、聚乙烯吡咯烷酮链和季铵阳离子侧链端基具有更高的摇摆或伸缩自由度和自由体积,遇水溶解或溶胀后,通过水化氢键作用的自组装即可形成亲水抗菌凝胶层。本发明提供的聚氨酯基多功能互穿网络聚合物在水、甲醇、乙醇、乙二醇、乙二醇甲醚、二甲亚砜、N‑甲基吡咯烷酮或N,N‑二甲基甲酰胺溶剂中溶胀或溶解后,会出现明显的微相分离现象。
Description
技术领域
本发明涉及一种多功能互穿网络聚合物及其制备方法,特别涉及具有亲水抗菌功能的聚氨酯基互穿网络聚合物,用作制备亲水抗菌聚氨酯材料的原料,或用于金属材料、棉织物、木材、聚氨酯材料、聚酰胺材料、硅酸盐材料或陶瓷材料表面的亲水抗菌改性,属于有机功能材料领域。
技术背景
聚氨酯(Polyurethanes,PUs)通常是由多元醇与多异氰酸酯发生加聚反应生成,属于典型的嵌段共聚物,可以多种产品形式:包括预聚物、弹性体、纤维、粘合剂、涂料或泡沫等应用于多领域;与其它高分子材料相比,聚氨酯材料具有分子结构易设计,软硬链节等可调,加工性能好、加工方式多样、机械性能优异等特性。通过对聚氨酯材料进行功能化改性,从而在保持聚氨酯优良性能的同时,并赋予其独特的生物学、光电磁热以及其它物理化学性质,已经成为扩大聚氨酯材料品种和应用领域的主要方法。目前流行的聚氨酯功能化方法有:共混改性、表面改性的涂覆和接枝、互穿网络,以及化学共聚。
互穿网络聚合物是由两种或两种以上的环状链聚合物互相贯穿而形成的混合物。两种以上的环状链聚合物链环结构的相互贯穿,互穿网络聚合物的环状链之间一般不形成化学键,依靠机械缠绕和链环向扣,形成宏观上均匀,微观上可能分相的共混体系,相界面较大,相互有很好的“协同效应”,而且起着“强迫互穿”的作用,达到抑制热力学上相分离的目的,互穿网络聚合物体系之间能够良好的分散,既可以充分展示各自特性,又可以形成功能特性的优势互补。专业人员熟知聚氨酯的大分子链结构具有闭合环状特征,是制备网络互穿聚合物的首选原料,所以现有的互穿网络聚合物大都是以聚氨酯为基础物质,与交联聚烯烃、环氧树脂、交联聚酯、交联聚酰胺等形成互穿网络聚合物。另外对制备聚氨酯原料(包括多元醇和多异氰酸酯)进行优化配用,可以制得胶粘强度、回弹性、柔韧性、亲水、抗菌和生物相容性等变化多样的聚氨酯产品。
为此,本发明提供一种聚氨酯基多功能互穿网络聚合物,本发明所述聚氨酯基多功能互穿网络聚合物指的是交联聚氨酯(Ⅰ)和多功能聚氨酯(Ⅱ)的互穿网络聚合物。所述交联聚氨酯(Ⅰ)是以聚合物多元醇、多异氰酸酯和扩链剂为原料制成的。所述多功能聚氨酯(Ⅱ)是由聚乙二醇单烷基醚、单端羟基聚乙烯吡咯烷酮、端羟基聚醚季铵盐与多异氰酸酯三聚体制成聚氨酯预聚物,再与季铵阳离子聚醚二元醇和扩链剂共混入所述交联聚氨酯(Ⅰ)溶液中,完成逐步加聚反应后制得的。所以侧链悬挂聚乙二醇链、聚乙烯吡咯烷酮和季铵阳离子聚醚的多功能聚氨酯(Ⅱ)和交联聚氨酯(Ⅰ)互穿网络混合物是按照顺序聚合方法制成的。
本发明提供的聚氨酯基多功能互穿网络聚合物具有多种有益效能:
①本发明所述聚氨酯基多功能互穿网络聚合物中的多功能聚氨酯(Ⅱ)大分子主链上悬挂的聚乙二醇链、聚乙烯吡咯烷酮链和季铵阳离子聚醚链具有优异的生物相容性、亲肤亲水和抗菌杀菌功能,所述多功能聚氨酯(Ⅱ)具有聚氨酯基大分子表面活性剂、高分子抗菌剂的功能。
②由于本发明所述交联聚氨酯(Ⅰ)的憎水特性和多功能聚氨酯(Ⅱ)的强亲水性,造成所述聚氨酯基多功能互穿网络聚合物具有典型的两亲特性,在水、甲醇、乙醇、乙二醇、乙二醇甲醚、二甲亚砜、N-甲基吡咯烷酮或N,N-二甲基甲酰胺溶剂中溶胀或溶解后,会出现明显的微相分离现象。
③本发明所述的聚氨酯基多功能互穿网络聚合物中的多功能聚氨酯(Ⅱ)大分子主链上悬挂的聚乙二醇链、聚乙烯吡咯烷酮链和季铵阳离子聚醚链相对具有更高的摇摆或伸缩自由度和自由体积,遇水溶解溶胀后,通过水化氢键作用的自组装即可形成亲水抗菌凝胶。
发明内容
本发明目的是要提供一种聚氨酯基多功能互穿网络聚合物,用作制备亲水抗菌聚氨酯材料的原料,或用于金属材料、棉织物、木材、聚氨酯材料、聚酰胺材料、硅酸盐材料或陶瓷材料表面的亲水抗菌改性,产生持久的亲水防雾和杀菌抗污功能。
为了实现上述目的,本发明提供的一种聚氨酯基多功能互穿网络聚合物,是通过以下步骤制得的:
步骤一:交联聚氨酯(Ⅰ)的制备
将聚合物多元醇和扩链剂加入反应釜中,于80~120℃真空干燥除水2~24小时,此后将反应釜中物料降温至室温,N2保护搅拌下,加入有机锡催化剂和有机胺催化剂,后连续加入多异氰酸酯和有机溶剂的混合物,控制反应釜中物料温度50~90℃,2~10小时后完成逐步加聚反应,制得交联聚氨酯(Ⅰ)溶液,备用。
其中聚合物多元醇指的是质均分子量在150~6000之间的聚醚多元醇、聚烯烃多元醇、聚酯多元醇、聚硅氧烷多元醇、植物油基多元醇中的一种或两种以上;
所述聚合物多元醇是合成交联聚氨酯(Ⅰ)的基础原料,聚合物多元醇的种类和其分子链的长短决定了交联聚氨酯(Ⅰ)的耐水解性、光稳定性、柔性、粘结强度特性;通过调控选用分子链长短或选用不同种类的聚合物多元醇以获得预期的性能。
所述扩链剂指的是甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷或三乙醇胺中的一种;这些小分子扩链剂含有三个以上的羟基,与多异氰酸酯反应后,能够提高交联聚氨酯(Ⅰ)结构中硬段的含量,并使得交联聚氨酯(Ⅰ)间具有部分交联结构特征,从而提高交联聚氨酯(Ⅰ)的硬度和耐磨性能。
所述有机锡催化剂指的是二丁基锡二月桂酸酯、辛酸亚锡、草酸亚锡、二丁基二马来酸锡、二(十二烷基硫)二丁基锡或二醋酸二丁基锡中的一种。
所述有机胺催化剂指的是三乙胺、对二甲氨基吡啶、N,N-二甲基乙醇胺、N,N-二甲基甲酰胺、三乙烯二胺、N,N-二烷基哌嗪、1-烷基咪唑、1,8-二氮杂双环[5.4.0]十一碳-7-烯、三乙烯二胺羧酸盐、N,N-二烷基哌嗪羧酸盐或1-烷基咪唑羧酸盐中的一种,其中所述烷基指的是C1-C18烷基。
所述多异氰酸酯指的是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯、四甲基苯二甲苯二异氰酸酯、1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或三甲基己烷二异氰酸酯中的一种;
所述多异氰酸酯是合成交联聚氨酯(Ⅰ)的基础原料,其所含NCO基能够与含羟基或氨基的聚合物多元醇或扩链剂起逐步加成聚合反应,从而生成所需要的交联聚氨酯,并具有交联网络结构特征。本发明所述甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯、四甲基苯二甲苯二异氰酸酯均属于芳香族多异氰酸酯,选用芳香族多异氰酸酯作为合成交联聚氨酯(Ⅰ)的基础原料,有利于提高其硬段质量;如若制备光稳定高的交联聚氨酯(Ⅰ),优选脂肪族多异氰酸酯包括1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或三甲基己烷二异氰酸酯作为合成交联聚氨酯(Ⅰ)的基础原料。
所述有机溶剂选自丙酮、丁酮、环己酮、四氢呋喃、1,4-二氧六环、氯苯、氯仿、1,2-二氯乙烷、甲苯、二甲苯、十氢萘、乙酸乙酯、N-甲基吡咯烷酮、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜中的一种或两种以上;
所述聚合物多元醇、多异氰酸酯、扩链剂、有机锡催化剂、有机胺催化剂和有机溶剂的用量质量比30~300/40~120/1~30/0.02~5/0.5~5/1~300。
步骤二:预聚物(A)的制备
将多异氰酸酯三聚体和有机溶剂的混合物加入反应釜中,再将已经干燥处理过的聚乙二醇单烷基醚、有机锡催化剂和有机胺催化剂加入反应釜中,N2保护搅拌下,控制反应釜内物料温度为50~90℃,控制逐步加聚反应时间2~8小时;此后采用二丁胺反滴定分析方法测得其中的-NCO值接近预定值时,将反应釜中物料温度降至室温,即制得预聚物溶液(A),备用;
其中所述多异氰酸酯三聚体指的是甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体、1,6-己二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体、五亚甲烷二异氰酸酯三聚体中的一种;
所述多异氰酸酯三聚体分子结构中含有三个NCO基团,依照NCO/OH=3:1的配比与聚乙二醇单烷基醚进行加成反应,制得所述预聚物分子结构中还有两个-NCO基团,目的是利用其与所述季铵阳离子二元醇再进行逐步加聚反应,形成具有网格结构特征的功能性聚氨酯。
所述有机溶剂选自丙酮、丁酮、环己酮、四氢呋喃、1,4-二氧六环、氯苯、氯仿、1,2-二氯乙烷、甲苯、二甲苯、十氢萘、乙酸乙酯、N-甲基吡咯烷酮、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜中的一种或两种以上;
所述聚乙二醇单烷基醚指的是质均分子量为600~6000的聚乙二醇单烷基醚,所述烷基指的是C1-C18的烃基;
所述聚乙二醇单烷基醚按照OH/NCO=1:3的摩尔配比与所述多异氰酸酯三聚体进行加成反应后,制得的聚氨酯预聚物分子结构中含有两个-NCO基团,又含有端烷氧基聚醚链。其中所述两个-NCO基团与所述季铵阳离子二元醇进行逐步加聚反应,形成具有网格结构特征的功能聚氨酯;所述端烷氧基聚醚链悬挂在所述功能聚氨酯主链上,所述端烷氧基聚醚既具有两亲性特性,又具有相对高的自由度和自由体积。
所述有机锡催化剂指的是二丁基锡二月桂酸酯、辛酸亚锡、草酸亚锡、二丁基二马来酸锡、二(十二烷基硫)二丁基锡或二醋酸二丁基锡中的一种;
所述有机胺催化剂指的是三乙胺、对二甲氨基吡啶、N,N-二甲基乙醇胺、N,N-二甲基甲酰胺、三乙烯二胺、N,N-二烷基哌嗪、1-烷基咪唑、1,8-二氮杂双环[5.4.0]十一碳-7-烯、三乙烯二胺羧酸盐、N,N-二烷基哌嗪羧酸盐或1-烷基咪唑羧酸盐中的一种,其中所述烷基指的是C1-C18烷基;
所述聚乙二醇单烷基醚、多异氰酸酯三聚体、有机锡催化剂、有机胺催化剂和有机溶剂的用量质量比30~300/40~200/0.02~5/0.5~5/1~300。
步骤三:预聚物(B)的制备
将多异氰酸酯三聚体和有机溶剂的混合物加入反应釜中,再将已经干燥处理过的端羟基聚乙烯吡咯烷酮和有机溶剂,以及有机锡催化剂和有机胺催化剂加入反应釜中,N2保护搅拌下,控温反应釜内物料温度50~90℃,控制逐步加聚反应时间2~8小时;此后采用二丁胺反滴定分析方法测得其中的NCO值接近预定值时,将反应釜中物料温度降至室温,即制得预聚物溶液(B),备用;
其中所述多异氰酸酯三聚体指的是甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体、1,6-己二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体、五亚甲烷二异氰酸酯三聚体中的一种;
所述多异氰酸酯三聚体分子结构中含有三个-NCO基团,依照NCO/OH=3:1的摩尔配比与端羟基聚乙烯吡咯烷酮进行加成反应,制得所述预聚物分子结构中还有两个NCO基团,目的是利用其与所述季铵阳离子二元醇再进行逐步加聚反应,形成具有网格结构特征的功能性聚氨酯。
所述端羟基聚乙烯吡咯烷酮指的是质均分子量为600~6000的单端羟基聚乙烯吡咯烷酮;所述有机溶剂选自丙酮、丁酮、环己酮、四氢呋喃、1,4-二氧六环、氯苯、氯仿、1,2-二氯乙烷、甲苯、二甲苯、十氢萘、乙酸乙酯、N-甲基吡咯烷酮、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜中的一种或两种以上;
所述端羟基聚乙烯吡咯烷酮按照OH/NCO=1:3的摩尔配比与所述多异氰酸酯三聚体进行加成反应后,制得的聚氨酯预聚物分子结构中含有两个-NCO基团,又含有聚乙烯吡咯烷酮端链。其中所述两个-NCO基团与所述季铵阳离子二元醇进行逐步加聚反应,形成具有网格结构特征的功能聚氨酯;所述聚乙烯吡咯烷酮端链悬挂在所述功能聚氨酯主链上,所述聚乙烯吡咯烷酮链既具有两亲性特性、吸湿性、毒性很低、生理相溶性,又具有相对高的自由度和自由体积,能够产生水凝胶体保护作用。
所述有机锡催化剂指的是二丁基锡二月桂酸酯、辛酸亚锡、草酸亚锡、二丁基二马来酸锡、二(十二烷基硫)二丁基锡或二醋酸二丁基锡中的一种;
所述有机胺催化剂指的是三乙胺、对二甲氨基吡啶、N,N-二甲基乙醇胺、N,N-二甲基甲酰胺、三乙烯二胺、N,N-二烷基哌嗪、1-烷基咪唑、1,8-二氮杂双环[5.4.0]十一碳-7-烯、三乙烯二胺羧酸盐、N,N-二烷基哌嗪羧酸盐或1-烷基咪唑羧酸盐中的一种,所述烷基指的是C1-C18的烷基;
所述端羟基聚乙烯吡咯烷酮、多异氰酸酯三聚体、有机锡催化剂、有机胺催化剂和有机溶剂的用量质量比30~300/40~200/0.2~5/0.5~5.0/1~300;
步骤四:聚氨酯基多功能互穿网络聚合物的制备
将步骤一制得的交联聚氨酯(Ⅰ)溶液、步骤二制得的预聚物(A)溶液、步骤三制得的预聚物(B)溶液和脱水干燥过的季铵阳离子聚醚二元醇和扩链剂加入反应釜中,N2保护下搅拌均匀后,控温反应釜内物料温度50~90℃,控制逐步加聚反应时间2~12小时,制得所述聚氨酯基多功能互穿网络聚合物;
其中所述季铵阳离子聚醚二元醇具有通式(1)所示结构:
其中通式(1)中R选自C1~C18的烃基中的一种,X-指的是Cl-或Br-,n或m指的是2~200中的自然数;
所述扩链剂指的是甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷或三乙醇胺中的一种;其中这些小分子扩链剂含有三个以上的羟基,与多异氰酸酯三聚体反应后,能够提高多功能聚氨酯(Ⅱ)结构中硬段的含量,并使得聚氨酯(Ⅱ)间具有部分交联结构特征,从而提高所述多功能聚氨酯(Ⅱ)的硬度和耐磨性能。
所述交联聚氨酯(Ⅰ)溶液、步骤二制得的预聚物(A)溶液、步骤三制得的预聚物(B)溶液、季铵阳离子聚醚二元醇和扩链剂的用量质量比为200~600/30~300/30~300/60~120/1~30。
具体实施方式
下面结合具体实施方式对本发明内容进行详细说明。
实施例1聚醚型聚氨酯多功能互穿网络聚合物-1的制备
步骤一:聚醚型聚氨酯(Ⅰ-1)的制备
将25公斤山东蓝星东大化工有限责任公司产的均分子量2000的聚醚二元醇DL-2000D和3.5公斤三羟甲基乙烷加入反应釜中,于100℃真空干燥除水2.5小时,此后将反应釜中物料降温至室温,N2保护搅拌下,再加入0.02公斤二丁基锡二月桂酸酯和0.05公斤三乙烯二胺,搅拌均匀后连续加入30公斤甲苯二异氰酸酯(TDI80/20)和10公斤脱水丙酮的混合物,逐渐提高反应釜中物料温度至50~65℃反应1小时,70~80℃反应2小时,制得聚醚型聚氨酯(Ⅰ-1)的粘稠状溶液,备用。
步骤二:预聚物(A-1)的制备
将山东万华公司生产固含量约为50%的6950F牌号甲苯异氰酸酯三聚体20公斤加入反应釜中,再将已经干燥处理过的5.6公斤聚乙二醇2000单甲醚、0.01公斤二丁基锡二月桂酸酯和0.03公斤三乙胺加入反应釜中,N2保护搅拌下,控制反应釜内物料温度为50~60℃,控制逐步加聚反应时间2~6小时;此后采用二丁胺反滴定分析方法测得其中的-NCO值接近4.5%时,将反应釜中物料温度降至室温,即制得预聚物溶液(A-1),备用;
步骤三:预聚物(B-1)的制备
将山东万华公司生产固含量约为50%的6950F牌号甲苯异氰酸酯三聚体20公斤加入反应釜中,再将已经干燥处理过的13公斤质均分子量为2000的单端羟基聚乙烯吡咯烷酮和和7公斤脱水丙酮的混合物,以及0.01公斤二丁基锡二月桂酸酯和0.03公斤三乙胺加入反应釜中,N2保护搅拌下,控温反应釜内物料温度50~60℃,控制逐步加聚反应时间2~6小时;此后采用二丁胺反滴定分析方法测得其中的-NCO值接近3.8%时,将反应釜中物料温度降至室温,即制得预聚物溶液(B-1),备用;
步骤四:聚醚型聚氨酯多功能互穿网络聚合物-1的制备
常温下,将步骤一制得的聚氨酯网络(Ⅰ-1)的粘稠状溶液约60公斤、步骤二制得的预聚物溶液(A-1)约25公斤、步骤三制得的预聚物溶液(B-1)约40公斤、已脱水干燥过的季铵阳离子聚醚二元醇式(1)6.5公斤和4.5公斤三羟甲基乙烷以及5公斤丙酮的混合物加入反应釜中,N2保护下搅拌均匀后,逐渐提高反应釜中物料温度至50~55℃反应2小时,70~80℃反应4小时,制得所述聚醚型聚氨酯基多功能互穿网络聚合物-1的淡黄色粘稠状胶液。
其中所述季铵阳离子聚醚二元醇式(1)所示结构:
其中所述式(1)中的n+m等于20。
实施例2聚醚型聚氨酯多功能互穿网络聚合物-2的制备
依照实施例1的步骤和方法,将实施例1步骤一中山东东大蓝星化工有限责任公司产的均分子量2000的聚醚二元醇DL-2000D改换为聚乙二醇-2000(PEG-2000,江苏海安石油化工厂),步骤二的甲苯异氰酸酯三聚体改换为德国拜耳产的1,6-己二异氰酸酯三聚体,步骤四中的季铵阳离子聚醚二元醇式(1)改换为季铵阳离子二元醇聚醚(式2),即可制得所述聚氨酯基多功能互穿网络聚合物-2淡黄色粘稠状胶液。
其中所述季铵阳离子聚醚二元醇式(2)所示结构:
其中所述式(2)中的n+m等于20。
实施例3聚酯型聚氨酯多功能互穿网络聚合物-1的制备
依照实施例1的步骤和方法,将实施例1步骤一中山东东大蓝星化工有限责任公司产的均分子量2000的聚醚二元醇DL-2000D改换为聚己二酸乙二醇酯-2000(山东摩尔化工有限公司),步骤二的甲苯异氰酸酯三聚体改换为德国拜耳产的1,6-己二异氰酸酯三聚体,即可制得所述聚酯型聚氨酯基多功能互穿网络聚合物-1的淡黄色粘稠状胶液。
实施例4聚烯烃型聚氨酯多功能互穿网络聚合物-1的制备
依照实施例1的步骤和方法,将实施例1步骤一中山东东大蓝星化工有限责任公司产的均分子量2000的聚醚二元醇DL-2000D改换为端羟基聚丁二烯二元醇-4000(深圳宏元新材料科技有限公司),步骤二的甲苯异氰酸酯三聚体改换为德国拜耳产的1,6-己二异氰酸酯三聚体,即可制得所述聚烯烃型聚氨酯基多功能互穿网络聚合物-1的淡黄色粘稠状胶液。
实施例5聚醚型聚氨酯多功能互穿网络聚合物-3的制备
依照实施例1的步骤和方法,将实施例1步骤一中山东东大蓝星化工有限责任公司产的均分子量2000的聚醚二元醇DL-2000D改换为聚乙二醇-2000(PEG-2000,江苏海安石油化工厂),步骤一中的三羟甲基乙烷改换为三乙醇胺,步骤二的甲苯异氰酸酯三聚体改换为德国拜耳产的1,6-己二异氰酸酯三聚体,即可制得所述聚醚型聚氨酯基多功能互穿网络聚合物-3的淡黄色粘稠状胶液。
实施例6聚醚型聚氨酯多功能互穿网络聚合物-4的制备
依照实施例1的步骤和方法,将实施例1步骤一中山东东大蓝星化工有限责任公司产的均分子量2000的聚醚二元醇DL-2000D改换为聚乙二醇-2000(PEG-2000,江苏海安石油化工厂),步骤一中的三羟甲基乙烷改换为三乙醇胺,步骤二的甲苯异氰酸酯三聚体改换为德国拜耳产的1,6-己二异氰酸酯三聚体,步骤四中的三羟甲基乙烷改换为三乙醇胺,即可制得所述聚醚型聚氨酯基多功能互穿网络聚合物-4的淡黄色粘稠状胶液。
实施例7聚氨酯多功能互穿网络聚合物的特性
分别称取实施例1~6中的所述聚氨酯基多功能互穿网络聚合物30克倒入聚四氟乙烯托盘中,置入真空干燥箱中60℃真空干燥后制得薄片,剪切成长*宽*厚为5*5*0.1cm的薄片恒重(W1)后,分别浸渍在去离子水和质量百分浓度为5%的盐酸中,2小时后捞出擦干称重(W2),由(W2-W1)/W1计算其吸水膨胀率,其结果见表1。
表1聚氨酯基多功能互穿网络聚合物的特性
Claims (10)
1.一种聚氨酯基多功能互穿网络聚合物,其特征在于是通过以下步骤制得的:
步骤一:交联聚氨酯(Ⅰ)的制备
将聚合物多元醇和扩链剂加入反应釜中,于80~120℃真空干燥除水2~24小时,此后将反应釜中物料降温至室温,N2保护搅拌下,加入有机锡催化剂和有机胺催化剂,后连续加入多异氰酸酯和有机溶剂的混合物,控制反应釜中物料温度50~90℃,2~10小时后完成逐步加聚反应,制得交联聚氨酯(Ⅰ)溶液,备用;
其中所述聚合物多元醇、多异氰酸酯、扩链剂、有机锡催化剂、有机胺催化剂和有机溶剂的用量质量比30~300/40~120/1~30/0.02~5/0.5~5/1~300;
步骤二:预聚物(A)的制备
将多异氰酸酯三聚体和有机溶剂的混合物加入反应釜中,再将已经干燥处理过的聚乙二醇单烷基醚、有机锡催化剂和有机胺催化剂加入反应釜中,N2保护搅拌下,控制反应釜内物料温度为50~90℃,控制逐步加聚反应时间2~8小时;此后采用二丁胺反滴定分析方法测得其中的-NCO值接近预定值时,将反应釜中物料温度降至室温,即制得预聚物溶液(A),备用;
其中所述聚乙二醇单烷基醚、多异氰酸酯三聚体、有机锡催化剂、有机胺催化剂和有机溶剂的用量质量比30~300/40~200/0.02~5/0.5~5.0/1~300;
步骤三:预聚物(B)的制备
将多异氰酸酯三聚体和有机溶剂的混合物加入反应釜中,再将已经干燥处理过的端羟基聚乙烯吡咯烷酮和有机溶剂,以及有机锡催化剂和有机胺催化剂加入反应釜中,N2保护搅拌下,控温反应釜内物料温度50~90℃,2~8小时后完成加成反应;此后采用二丁胺反滴定分析方法测得其中的-NCO值接近预定值时,将反应釜中物料温度降至室温,即制得预聚物溶液(B),备用;
其中所述端羟基聚乙烯吡咯烷酮、多异氰酸酯三聚体、有机锡催化剂、有机胺催化剂和有机溶剂的用量质量比30~300/40~200/0.02~5/0.5~5/1~300;
步骤四:聚氨酯基多功能互穿网络聚合物的制备
将步骤一制得的交联聚氨酯(Ⅰ)溶液、步骤二制得的预聚物(A)溶液、步骤三制得的预聚物(B)溶液和脱水干燥过的季铵阳离子聚醚二元醇和扩链剂加入反应釜中,N2保护下搅拌均匀后,控温反应釜内物料温度50~90℃,2~12小时后完成逐步加聚反应,制得所述聚氨酯基多功能互穿网络聚合物;
其中所述季铵阳离子聚醚二元醇具有通式(1)所示结构:
其中通式(1)中R选自C1~C18的烃基中的一种,X-指的是Cl-或Br-,n或m指的是2~200中的自然数;
所述交联聚氨酯(Ⅰ)溶液、步骤二制得的预聚物(A)溶液、步骤三制得的预聚物(B)溶液、季铵阳离子聚醚二元醇和扩链剂的用量质量比为200~600/30~300/30~300/60~120/1~30。
2.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述聚合物多元醇指的是质均分子量在150~6000之间的聚醚多元醇、聚烯烃多元醇、聚酯多元醇、聚硅氧烷多元醇、植物油基多元醇中的一种或两种以上。
3.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述扩链剂指的是甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷或三乙醇胺中的一种。
4.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述有机锡催化剂指的是二丁基锡二月桂酸酯、辛酸亚锡、草酸亚锡、二丁基二马来酸锡、二(十二烷基硫)二丁基锡或二醋酸二丁基锡中的一种。
5.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述有机胺催化剂指的是三乙胺、对二甲氨基吡啶、N,N-二甲基乙醇胺、N,N-二甲基甲酰胺、三乙烯二胺、N,N-二烷基哌嗪、1-烷基咪唑、1,8-二氮杂双环[5.4.0]十一碳-7-烯、三乙烯二胺羧酸盐、N,N-二烷基哌嗪羧酸盐或1-烷基咪唑羧酸盐中的一种,其中所述烷基指的是C1-C18烷基。
6.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述多异氰酸酯指的是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯、四甲基苯二甲苯二异氰酸酯、1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或三甲基己烷二异氰酸酯中的一种。
7.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述有机溶剂选自丙酮、丁酮、环己酮、四氢呋喃、1,4-二氧六环、氯苯、氯仿、1,2-二氯乙烷、甲苯、二甲苯、十氢萘、乙酸乙酯、N-甲基吡咯烷酮、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜中的一种或两种以上。
8.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述多异氰酸酯三聚体指的是甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体、1,6-己二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体、五亚甲烷二异氰酸酯三聚体中的一种。
9.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述聚乙二醇单烷基醚指的是质均分子量为600~6000的聚乙二醇单烷基醚,所述烷基指的是C1-C18烃基。
10.依照权利要求1所述的一种聚氨酯基多功能互穿网络聚合物,其特征在于所述端羟基聚乙烯吡咯烷酮指的是质均分子量为600~6000的单端羟基聚乙烯吡咯烷酮。
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