CN106589306A - 一种制备高强度改性聚氨酯复合材料的方法及产品 - Google Patents

一种制备高强度改性聚氨酯复合材料的方法及产品 Download PDF

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CN106589306A
CN106589306A CN201611185975.1A CN201611185975A CN106589306A CN 106589306 A CN106589306 A CN 106589306A CN 201611185975 A CN201611185975 A CN 201611185975A CN 106589306 A CN106589306 A CN 106589306A
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欧宝立
陈美龙
李政峰
郭艳
颜建辉
刘清泉
刘欢
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Abstract

本发明涉及一种制备高强度改性聚氨酯复合材料的方法：以含苯环的多羟基苯酐聚酯多元醇作为合成高粘度聚氨酯的单体，同时在聚合反应过程中加入少量二羟基笼形低聚倍半硅氧烷共同反应，在聚氨酯进行初步预聚合反应之后，加入含极性基团氰基的扩链剂N‑( 2‑氰乙基) 二乙醇胺进行扩链反应。为进一步改善聚氨酯复合粘合剂的抗拉伸强度等力学性能以及抗静电能力，形成复合材料的内部三维网状结构，将已氧化的碳纳米管通过聚氨酯末端残留异氰酸酯基接枝到POSS/聚氨酯材料当中，最终达到合成一种综合性能优越的高强度聚氨酯复合材料。

Description

一种制备高强度改性聚氨酯复合材料的方法及产品
技术领域
本发明属于高分子复合材料领域，涉及一种高强度改性聚氨酯复合材料及其制备方法。
背景技术
聚氨酯胶粘剂（简称PU胶）具有优良的粘接性、柔韧性、耐油、耐冲击、耐磨、耐低温等特性；其品种繁多，分子结构可调性强，粘接适用范围广，自德国Bayer公司工业化六十多年来，得到了迅速的发展。通用型PU胶是我国应用广泛的聚氨酯胶粘剂，代表性产品是PU101胶。一般以聚己二酸乙二醇酯等与甲苯二异氰酸酯反应制得端羟基PU树脂溶于有机溶剂为主成分；以三羟甲基丙烷与甲苯二异氰酸酯加成物的醋酸乙酯溶液为固化剂；其可将金属、塑料、织物等不同材料较好的的粘接起来。然而其普遍存在有粘结强度不够，耐热性差，易老化，抗化学腐蚀性能力弱，不具抗静电能力等不足，随着人们生活水平的提高，市场上对于粘合剂的性能要求越来越高，研发制备一种综合性能优异的高强度聚氨酯粘合剂以满足市场需求具有重大意义。
苯酐聚酯多元醇属于芳烃聚酯多元醇，同一般聚酯或聚醚多元醇相比，其由于在分子结构中引入了苯环，从而在较大程度上提高了聚氨酯粘合剂的强度，由其制备的胶黏剂具有阻燃性、刚性和耐化学腐蚀的优良性能，能够应用于包括金属与热绝缘材料、塑料与热绝缘材料以及金属与塑料等复合粘结（冯涛，韩胜利，杨足明，贾云龙，苯酐聚酯多元醇制备高强度聚氨酯胶粘剂，粘结，2012,11(3),42-44）。
聚氨酯中的大分子多元醇结构、异氰酸酯种类、小分子扩链剂类型等都影响了聚氨酯的粘结能力，氰基( -CN) 为强极性基团，有利于形成氢键作用，研究表明在聚氨酯结构中引入氰基可明显提高聚氨酯粘合材料的粘结能力（张霁，许飞，戴家兵，极性基团(-CN)对水性聚氨酯涂料附着力的影响，上海涂料，2012,50（6）,10-13）。
POSS热稳定性好、单分散性良好且密度低，是具有广泛应用前景的有机-无机化合物。通过其结构上的单个或多个可反应性官能团进行表面改性、接枝及聚合反应，制备POSS基纳米复合材料，达到提高材料的热性能、阻燃和抗氧化性能等目的。相比于传统的填充剂材料，向聚合物体系中加入很少量的POSS便会使复合材料的性能得到明显提高。
碳纳米管作为纳米尺寸的碳材料,具有极大的比表面积、良好的导电性以及优秀的机械性能等特性。碳纳米管/高分子复合材料形成三维网状结构, 选择合适的方法制备出碳纳米管复合材料，通过它们之间的协同效应，使其表现出比任意一种单一材料更加优异的性能，例如更好的各向同性导热性、各向同性导电性、三维空间微孔网络等特性。基于以上性质，使得碳纳米复合材料在很多领域有着极大的应用前景（Hongjie Dai ,CarbonNanotubes:Synthesis, Integration, and Properties，Acc. Chem. Res., 2002, 35(12), 1035-1044）。
发明内容
本研究的目的是解决目前聚氨酯粘合材料普遍存在的粘结强度不够，船舰等表面涂覆材料强度较差、耐热性差，易老化，抗化学腐蚀性能力弱，不具抗静电能力等问题，提供一种高效制备高强度改性聚氨酯复合材料的方法。
为实现上述目的，本发明采用的技术方案为：一种高强度改性聚氨酯复合材料制备的方法，包括以下步骤：
（1）先将原始碳纳米管加入到浓硫酸和浓硝酸的混合溶液中进行高温回流，然后用蒸馏水洗涤稀释至中性，抽滤后干燥，最后研磨得氧化碳纳米管粉末，备用；
（2）扩链剂N-( 2-氰乙基) 二乙醇胺的合成：首先将二乙醇胺加入到容器中，在低温条件下缓慢滴入丙烯腈，然后升温进行反应，获得透明的N-( 2-氰乙基) 二乙醇胺备用；
（3）将多羟基苯酐聚酯多元醇投入到容器中，加热并真空减压脱水，降温后加入二羟基笼形低聚倍半硅氧烷(二羟基POSS)混合，然后加入多亚甲基多苯基多异氰酸酯，通入氮气，升温并保持体系反应；冷却后加入步骤（2）制备的N-( 2-氰乙基) 二乙醇胺、丙酮和催化剂辛酸亚锡，进行扩链反应；反应后加入步骤（1）制备的氧化碳纳米管，反应得高强度改性聚氨酯复合材料。
作为优选，步骤（3）中，将多羟基苯酐聚酯多元醇投入到容器中，加热并真空减压脱水1 h，降温后加入二羟基笼形低聚倍半硅氧烷(二羟基POSS)搅拌混合，然后边搅拌边滴加多亚甲基多苯基多异氰酸酯，通入氮气，升温并保持体系反应1 h；冷却后加入步骤（2）制备的N-( 2-氰乙基) 二乙醇胺、丙酮和催化剂辛酸亚锡，进行扩链反应；反应1 h后加入步骤（1）制备的氧化碳纳米管，反应2-3 h得高强度改性聚氨酯复合材料。
一种如权利要求1所述的方法制备高强度改性聚氨酯复合材料。
本发明创新性地以含苯环的多羟基苯酐聚酯多元醇作为合成高粘度聚氨酯的单体，同时在聚合反应过程中加入少量二羟基笼形低聚倍半硅氧烷(二羟基POSS)共同反应，提高了聚氨酯高分子材料的阻燃性和抗氧化性。在聚氨酯进行初步预聚合反应之后，加入含极性基团氰基的扩链剂N-( 2-氰乙基) 二乙醇胺进行扩链反应，提高了聚氨酯高分子粘合剂的粘结强度。为进一步改善聚氨酯复合粘合剂的抗拉伸强度等力学性能以及抗静电能力，形成复合材料的内部三维网状结构，将已氧化的碳纳米管通过聚氨酯末端残留异氰酸酯基接枝到POSS/聚氨酯材料当中，最终达到合成一种综合性能优越的高强度聚氨酯复合材料。并且，在本发明中的连贯性制备过程中，反应简洁，反应速率较快。发明产品性质稳定，性能优良且产率较高，在用于船舰表面高强度涂层、工业高负荷金属零件粘结、电子通讯精密仪器粘结等众多领域有巨大应用潜力。
下面结合附图和具体实施例对本发明作进一步详细说明。
附图说明
图1为本发明制备高强度改性聚氨酯复合材料（曲线b）及分子结构无苯环单纯聚氨酯高分子材料红外光谱（曲线a）的对比红外光谱图。
图2为本发明制备高强度改性聚氨酯复合材料的实物图。
具体实施方式
实施例1：
称取2.0 g原始碳纳米管，加入到150 mL浓硫酸和50 mL浓硝酸的混合溶液中，在100℃下回流6 h，用蒸馏水稀释并抽滤，至滤液呈中性。于90℃中空干燥箱内干燥6 h，研磨得氧化碳纳米管粉末备用。将0.5 mol 二乙醇胺加入到250 mL 三口烧瓶中，缓慢滴入0.5mol 丙烯腈进行反应。滴加丙烯腈时温度维持在20 ℃，装上冷凝回流装置，升温至70 ℃反应1.5 h，获得扩链剂N-( 2-氰乙基)二乙醇胺备用。将10 mL多羟基苯酐聚酯多元醇加入到三口烧瓶中，加热至120℃真空减压脱水1 h，降温至60 ℃后加入3.0 g 1,3,5,7,9,11,13-苯基-15-二乙醇胺丙基笼形低聚倍半硅氧烷(羟基POSS)搅拌混合，然后边搅拌边滴加5mL多亚甲基多苯基多异氰酸酯，通入氮气,升温并保持体系在（80±5）℃反应1小时, 冷却在50 ℃（预聚）。加入0.5 mL N-( 2-氰乙基) 二乙醇胺、20mL丙酮和0.5 g催化剂辛酸亚锡，在75 ℃下进行扩链反应，反应过程中如果体系黏度过大，加入适量 Ac 进行调节。反应1 h后加入2.0 g氧化碳纳米管，反应2 h得POSS /聚氨酯接枝碳纳米管复合材料。如图1曲线b所示，本发明所制备的POSS/聚氨酯接枝碳纳米管复合材料红外光谱图中存在有，波数在1225-1235附近的聚酯C-O伸缩峰，波数在1600-1615附近的苯环C=C骨架伸缩振动峰，波数在1715-1750附近的酯基C=O强吸收峰，波数在2240-2280附近的-NCO特征吸收峰以及波数在2940处的-CH2、-CH3伸缩峰。对比分子结构无苯环单纯聚氨酯高分子材料红外光谱曲线a，表明POSS/聚氨酯接枝碳纳米管复合材料成功制备，高分子链中含苯环比例明显，其末端残留基团为-NCO。将制备的高强度粘合剂，涂抹在接触面积为2×6 cm-2的环氧树脂复合纤维板片上，干燥24 h后，经材料万能试验机做拉伸测试，其断裂拉伸强度为135.6 Mpa；放置在温度恒定为35℃的烘箱中14天，结果表明其稳定性良好，未出现老化现象。
实施例2：
称取2.0 g原始碳纳米管，加入到150 mL浓硫酸和50 mL浓硝酸的混合溶液中，在100℃下回流6 h，用蒸馏水稀释并抽滤，至滤液呈中性。于90℃中空干燥箱内干燥6 h，研磨得氧化碳纳米管粉末备用。将0.5 mol 二乙醇胺加入到250 mL 三口烧瓶中，缓慢滴入0.5mol 丙烯腈进行反应。滴加丙烯腈时温度维持在20 ℃，装上冷凝回流装置，升温至70 ℃反应1.5 h，获得扩链剂N-( 2-氰乙基)二乙醇胺备用。将10 mL多羟基苯酐聚酯多元醇加入到三口烧瓶中，加热至120℃真空减压脱水1 h，降温至60 ℃后加入2.0 g 1,3,5,7,9,11,13-苯基-15-二乙醇胺丙基笼形低聚倍半硅氧烷(羟基POSS)搅拌混合，然后边搅拌边滴加5mL多亚甲基多苯基多异氰酸酯，通入氮气,升温并保持体系在（80±5）℃反应1小时,冷却在50℃（预聚）。加入0.5 mL N-( 2-氰乙基) 二乙醇胺、20mL丙酮和0.5 g催化剂辛酸亚锡，在75℃下进行扩链反应，反应过程中如果体系黏度过大，加入适量 Ac 进行调节。反应1 h后加入1.0 g氧化碳纳米管，反应2 h得POSS /聚氨酯接枝碳纳米管复合材料。经红外光谱表征，表明POSS/聚氨酯接枝碳纳米管复合材料成功制备，高分子链中含苯环比例明显，其末端残留基团为-NCO。将制备的高强度粘合剂，涂抹在接触面积为2×6 cm-2的环氧树脂复合纤维板片上，干燥24 h后，经材料万能试验机做拉伸测试，其断裂拉伸强度为125.60Mpa；放置在温度恒定为35℃的烘箱中14天，结果表明其稳定性良好，未出现老化现象。
实施例3：
称取2.0 g原始碳纳米管，加入到150 mL浓硫酸和50 mL浓硝酸的混合溶液中，在100℃下回流6 h，用蒸馏水稀释并抽滤，至滤液呈中性。于90℃中空干燥箱内干燥6 h，研磨得氧化碳纳米管粉末备用。将0.5 mol 二乙醇胺加入到250 mL 三口烧瓶中，缓慢滴入0.5mol 丙烯腈进行反应。滴加丙烯腈时温度维持在20 ℃，装上冷凝回流装置，升温至70 ℃反应1.5 h，获得扩链剂N-( 2-氰乙基)二乙醇胺备用。将10 mL多羟基苯酐聚酯多元醇加入到三口烧瓶中，加热至120℃真空减压脱水1 h，降温至60 ℃后加入4.0 g 1,3,5,7,9,11,13-苯基-15-二乙醇胺丙基笼形低聚倍半硅氧烷(羟基POSS)搅拌混合，然后边搅拌边滴加5mL多亚甲基多苯基多异氰酸酯，通入氮气,升温并保持体系在（80±5）℃反应1小时,冷却在50℃（预聚）。加入0.5 mL N-( 2-氰乙基) 二乙醇胺、20mL丙酮和0.5 g催化剂辛酸亚锡，在75℃下进行扩链反应，反应过程中如果体系黏度过大，加入适量 Ac 进行调节。反应1 h后加入3.0 g氧化碳纳米管，反应2 h得POSS /聚氨酯接枝碳纳米管复合材料。经红外光谱表征，表明POSS/聚氨酯接枝碳纳米管复合材料成功制备，高分子链中含苯环比例明显，其末端残留基团为-NCO。将制备的高强度粘合剂，涂抹在接触面积为2×6 cm-2的环氧树脂复合纤维板片上，干燥24 h后，经材料万能试验机做拉伸测试，其断裂拉伸强度为118.3Mpa；放置在温度恒定为35℃的烘箱中14天，结果表明其稳定性良好，未出现老化现象。
上述实施例在以本发明技术方案为前提下进行实施，所给出的详细实施方式和过程，是对本发明的进一步说明，而不是限制本发明的范围。

Claims (3)

1.一种高强度改性聚氨酯复合材料制备的方法，其特征在于，包括以下步骤：
（1）先将原始碳纳米管加入到浓硫酸和浓硝酸的混合溶液中进行高温回流，然后用蒸馏水洗涤稀释至中性，抽滤后干燥，最后研磨得氧化碳纳米管粉末，备用；
（2）扩链剂N-( 2-氰乙基) 二乙醇胺的合成：首先将二乙醇胺加入到容器中，在低温条件下缓慢滴入丙烯腈，然后升温进行反应，获得透明的N-( 2-氰乙基) 二乙醇胺备用；
（3）将多羟基苯酐聚酯多元醇投入到容器中，加热并真空减压脱水，降温后加入二羟基笼形低聚倍半硅氧烷(二羟基POSS)混合，然后加入多亚甲基多苯基多异氰酸酯，通入氮气，升温并保持体系反应；冷却后加入步骤（2）制备的N-( 2-氰乙基) 二乙醇胺、丙酮和催化剂辛酸亚锡，进行扩链反应；反应后加入步骤（1）制备的氧化碳纳米管，反应得高强度改性聚氨酯复合材料。
2.根据权利要求1所述的高强度改性聚氨酯复合材料制备的方法，其特征在于，步骤（3）中，将多羟基苯酐聚酯多元醇投入到容器中，加热并真空减压脱水1 h，降温后加入二羟基笼形低聚倍半硅氧烷(二羟基POSS)搅拌混合，然后边搅拌边滴加多亚甲基多苯基多异氰酸酯，通入氮气，升温并保持体系反应1 h；冷却后加入步骤（2）制备的N-( 2-氰乙基) 二乙醇胺、丙酮和催化剂辛酸亚锡，进行扩链反应；反应1 h后加入步骤（1）制备的氧化碳纳米管，反应2-3 h得高强度改性聚氨酯复合材料。
3.一种如权利要求1所述的方法制备高强度改性聚氨酯复合材料。
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