CN106189192B - 一种凯夫拉纤维-聚氨酯复合发泡材料及其制备方法 - Google Patents

一种凯夫拉纤维-聚氨酯复合发泡材料及其制备方法 Download PDF

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CN106189192B
CN106189192B CN201610639437.9A CN201610639437A CN106189192B CN 106189192 B CN106189192 B CN 106189192B CN 201610639437 A CN201610639437 A CN 201610639437A CN 106189192 B CN106189192 B CN 106189192B
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谢义鹏
许钧强
康伦国
姚东生
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Shanghai Yirun New Material Technology Co.,Ltd.
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Abstract

本发明涉及一种凯夫拉纤维改性聚氨酯复合发泡材料，由A组分和B组分按照质量份配比1:0.8～1：1.8在常温下混合搅拌制备而得；其特征在于凯夫拉纤维的酰胺键可与异氰酸酯中的氰基发生化学反应，直接参与泡沫材料刚性骨架的形成过程，同时凯夫拉纤维与阻燃剂共同作用，在添加较少阻燃剂的前提下，大幅度提高聚氨酯泡沫的阻燃性，由于凯夫拉纤维的永久耐酸碱腐蚀与耐溶剂特性，本发明泡沫材料的耐酸碱腐蚀性与耐溶剂性等性能得到了较大幅度提高，使其更适宜应用到建筑材料、家具、汽车内饰、隔热板材等领域。

Description

一种凯夫拉纤维-聚氨酯复合发泡材料及其制备方法
技术领域
本发明属于高分子材料合成领域，具体涉及一种凯夫拉纤维改性聚氨酯复合发泡材料及其制备方法。
技术背景
聚氨酯是一种广泛应用的高分子材料，具有优异的物理机械性能及良好的耐水性。聚氨酯泡沫体是以树脂为基础，采用化学或物理方法在其内部产生无数小气孔而制成，孔孔相连的多孔聚氨酯海绵状泡沫材料体积密度小、比表面积大、吸附效率高，已经在催化剂载体、建筑、装饰、污水净化、血浆的过滤等方面得到了应用。
但聚氨酯材料仍然存在许多不足，在建筑领域，因聚氨酯材料所具有的保温隔热、防水、隔音等功能而应用广泛，但同时聚氨酯材料的强度低、阻燃性差等限制了其进一步推广。通过改性等手段增强聚氨酯发泡材料在性能方面的不足成为该领域的热点。
中国专利号CN201310430858.7公开了一种阻燃聚氨酯泡沫体及其制备方法，在现有聚氨酯泡沫配方中加入水玻璃替代传统氟氯烃发泡剂，可有效减少环境污染；同时水玻璃与无卤阻燃剂、石墨阻燃剂共同作用，提高聚氨酯的阻燃性，适宜应用到建筑材料、家具、保温材料、汽车座垫及内饰等领域。
中国专利号CN201410439154.0公开了一种低密度长玻纤纤维增强阻燃聚氨酯发泡材料及制备方法，制备方法为：无碱玻纤在高压浇注机混合头附近割长度5～20cm无碱长玻纤后，与偶联剂置反应釜反应0.5～2h，得玻纤初料；常温，将异氰酸酯、聚醚比例装干燥容器，搅拌，得混合原料；玻纤初料置混合原料中浸润，依次加阻燃剂、催化剂、发泡剂，混合均匀，得混合次料；混合次料注入模腔，经LFI工艺注射成型，得聚氨酯发泡材料。该方法所得聚氨酯发泡材料密度低、阻燃性好、力学性能佳，该方法操作简单、周期短、玻纤损耗低。
发明内容
凯夫拉纤维即聚对苯二甲酰对苯二胺纤维，是目前世界上规模化生产的综合性能最优异的高性能的有机纤维之一，具有优良的机械性能、绝缘性能和耐温、耐化学等性能，而且质量轻，可作为高性能复合材料的增强材料，被广泛应用于航空、航天、造船、汽车和建筑等领域。本发明的一种凯夫拉纤维-聚氨酯复合发泡材料将发挥凯夫拉纤维与聚氨酯材料二者的优点，制备出综合性能优异、应用更加广泛的新型复合发泡材料。
为克服现有技术的缺点和不足，本发明的首要目的旨在提供一种凯夫拉纤维-聚氨酯复合发泡材料。
本发明一种凯夫拉纤维-聚氨酯复合发泡材料，其特征在于凯夫拉纤维的酰胺键可与异氰酸酯类发生化学反应，直接参与泡沫材料的形成过程；其主要成分由A组分和B组分按照质量份比1:0.8～1:1.8经常温混合搅拌制备而得，A、B组分的组成及制备方法如下：
a、A组分的制备：将多异氰酸酯、增韧剂加入反应釜，室温条件下混合搅拌1～2h，即制得A组分；
b、B组分制备：将发泡剂、聚醚多元醇、聚酯多元醇、泡沫稳泡剂、催化剂、凯夫拉纤维、阻燃剂，加入反应釜，室温下混合搅拌1～2h，即制得B组分。
c、再将A组分和B组分按照质量比1:0.8～1：1.8混合，充分搅拌后，倒入模具中发泡、熟化，脱模，得到本发明凯夫拉纤维-聚氨酯复合材料泡沫体。
所述的A组分质量份组成为：异氰酸酯类80～150份、增韧剂10～30份。
其中，所述的异氰酸酯类为甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、多亚甲基多苯基多异氰酸酯PAPI中的至少一种；进一步的，优选多亚甲基多苯基多异氰酸酯PAPI。
所述的增韧剂为磷酸酯、柠檬酸酯、醋酸酯、邻苯二甲酸酯中的至少一种。
所述的B组分质量份组成为：发泡剂3～15份、聚醚多元醇30～55份、聚酯多元醇30～60份、催化剂0.1～0.5份、泡沫稳定剂2～5份、凯夫拉纤维10～60份、阻燃剂5～10份。
其中，所述的发泡剂为碳酸氢钠、偶氮二甲酰胺、碳酸氢钠、异戊烷、正戊烷、氟氯烃发泡剂中的一种或几种的组合；进一步的，优选碳酸氢钠。
所述的聚醚多元醇为聚氧化丙烯多元醇、聚四氢呋喃多元醇、四氢呋喃-氧化丙烯共聚多元醇或特种聚醚多元醇中一种或几种的组合。
所述的聚酯多元醇为脂肪族聚酯多元醇、芳香族聚酯多元醇、脂环族聚酯多元醇中的一种或几种的组合；进一步的，优选聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇或聚己内酯二元醇。
所述的催化剂为脂肪族胺类、芳香族胺类与有机金属催化剂中的至少一种；进一步的，优选二丁基锡二月桂酸锡或三乙烯二胺。
所述的泡沫稳定剂为有机硅泡沫稳定剂、磺酸基类泡沫稳定剂中的至少一种。
所述的凯夫拉纤维为凯夫拉纤维原丝、细度不同的凯夫拉纤维长丝或短丝中的至少一种；进一步的，优选Kevlar-49短纤维。
所述的阻燃剂为有机磷系阻燃剂、氮系阻燃剂、磷-卤系阻燃剂中的一种或几种的组合；进一步的，优选甲基膦酸二甲酯。
步骤c中所述的搅拌目的在于A、B组分混合均匀且具有可流动性，搅拌时间为5～60s，搅拌速度为600～1800rps/min。
本发明的一种凯夫拉纤维-聚氨酯复合发泡材料增强原理：一方面凯夫拉纤维作为刚性材料填充到聚氨酯泡沫材料中，起物理增强作用；另一方面，在催化剂作用下，凯夫拉纤维中比较活泼的活性较强的酰胺键与异氰酸酯中的氰基发生化学反应，直接参与泡沫材料的形成过程，使得泡沫材料形成强度更高的刚性骨架；在提高聚氨酯泡沫材料强度的同时，凯夫拉纤维与阻燃剂共同作用，在添加较少阻燃剂的前提下，大幅度提高聚氨酯泡沫的阻燃性；由于凯夫拉纤维的永久耐酸碱腐蚀与耐溶剂特性，本发明的泡沫材料的耐酸碱腐蚀性与耐溶剂性等性能得到了较大幅度提高，使其更适宜应用到建筑材料、家具、汽车内饰、隔热板材等领域。
具体实施方式
实施例1
a、A组分的制备：将二苯基甲烷二异氰酸酯120份、柠檬酸酯20份加入反应釜，室温条件下混合搅拌1～2h，制得A组分；
b、B组分制备：将发泡剂碳酸氢钠10份、聚四氢呋喃多元醇15份、聚氧化丙烯多元醇25份、己二酸丁二醇酯二元醇20份、聚醚改性聚硅氧烷泡沫稳泡剂4份、二乙烯三胺0.2份、凯夫拉纤维短纤40份、甲基膦酸二甲酯5份，加入反应釜，室温下混合搅拌1～2h，制得B组分。
c、再将A组分和B组分按比例混合，搅拌速度为600～1800rps/min充分搅拌30s后，倒入薄板模具中发泡、熟化，脱模，得到一种凯夫拉纤维-聚氨酯复合材料泡沫体。
按照上述实施例1方式将B组分中的凯夫拉纤维更换为细玻璃纤维短纤，所得发泡材料记为对比例1。
实施例2
a、A组分的制备：将TDI 90份、邻苯二甲酸酯16份加入反应釜，室温条件下混合搅拌1～2h，制得A组分；
b、B组分制备：将碳酸氢钠15份、聚四氢呋喃多元醇40份、己二酸丁二醇酯二元醇40份、聚碳酸酯二元醇或聚己内酯二元醇10份、醚改性聚硅油5份、二乙烯三胺0.3份、凯夫拉纤维短纤30份、甲基膦酸二甲酯5份，加入反应釜，室温下混合搅拌1～2h，制得B组分。
c、再将A组分和B组分按比例混合，搅拌速度为600～1800rps/min充分搅拌30s后，倒入薄板模具中发泡、熟化，脱模，得到一种凯夫拉纤维-聚氨酯复合材料泡沫体。
按照上述实施例2方式将B组分中的凯夫拉纤维更换为细玻璃纤维短纤，所得发泡材料记为对比例2。
实施例3
a、A组分的制备：将TDI 50份、MDI 70份、邻苯二甲酸酯20份加入反应釜，室温条件下混合搅拌1～2h，制得A组分；
b、B组分制备：将碳酸氢钠8份、四氢呋喃-氧化丙烯共聚多元醇12份、己二酸丁二醇酯二元醇40份、醚改性聚硅油5份、二丁基锡二月桂酸锡0.4份、凯夫拉纤维短纤50份、甲基膦酸二甲酯5份，加入反应釜，室温下混合搅拌1～2h，制得B组分。
c、再将A组分和B组分按比例混合，搅拌速度为600～1800rps/min充分搅拌30s后，倒入薄板模具中发泡、熟化，脱模，得到一种凯夫拉纤维-聚氨酯复合材料泡沫体。
按照上述实施例3方式将B组分中的凯夫拉纤维更换为超细玻璃纤维短纤，所得发泡材料记为对比例3。
本发明实施例中的样品与对比例中的样品技术性能，按照相关标准进行对比测试，结果如表1所示。
表1：实施例与对比例中的技术性能
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。

Claims (9)

1.一种凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述凯夫拉纤维-聚氨酯复合发泡材料，由A组分和B组分组成；所述A组分，其质量份组成为：多异氰酸酯80～150份、增韧剂10～30份；所述B组分，其质量份组成为：发泡剂3～15份、聚醚多元醇30～55份、聚酯多元醇30～60份、催化剂0.1～0.5份、泡沫稳定剂2～5份、凯夫拉纤维10～60份、阻燃剂5～10份；所述A组分与所述B组分的质量份配比为1:0.8～1:1.8；
其中，所述多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯中的至少一种；所述发泡剂为碳酸氢钠、偶氮二甲酰胺、异戊烷、正戊烷、氟氯烃发泡剂中的一种或几种的组合；所述聚醚多元醇为聚氧化丙烯多元醇、聚四氢呋喃多元醇、四氢呋喃-氧化丙烯共聚多元醇或特种聚醚多元醇中一种或几种的组合；所述聚酯多元醇为脂肪族聚酯多元醇、芳香族聚酯多元醇、脂环族聚酯多元醇中的一种或几种的组合；所述催化剂为脂肪族胺类、芳香族胺类、有机金属催化剂中的至少一种；所述泡沫稳定剂为有机硅泡沫稳定剂、磺酸基类泡沫稳定剂中的至少一种；所述凯夫拉纤维为凯夫拉纤维原丝、不同细度的凯夫拉纤维长丝或短丝中的至少一种；所述阻燃剂为有机磷系阻燃剂、氮系阻燃剂、磷-卤系阻燃剂中的一种或几种的组合。
2.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述多异氰酸酯为多亚甲基多苯基多异氰酸酯。
3.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述增韧剂为磷酸酯、柠檬酸酯、醋酸酯、邻苯二甲酸酯中的至少一种。
4.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述发泡剂为碳酸氢钠。
5.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯二元醇、聚己内酯二元醇中的至少一种。
6.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述催化剂为二丁基锡二月桂酸锡或三乙烯二胺。
7.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述凯夫拉纤维为Kevlar-49短纤维。
8.根据权利要求1所述的凯夫拉纤维-聚氨酯复合发泡材料，其特征在于：所述阻燃剂为甲基膦酸二甲酯。
9.一种如权利要求1所述凯夫拉纤维-聚氨酯复合发泡材料的制备方法，其特征在于：制备步骤如下：
a)、将多异氰酸酯、增韧剂加入反应釜，在室温条件下混合搅拌1～2h，得所述A组分；
b)、将发泡剂、聚醚多元醇、聚酯多元醇、泡沫稳定剂、催化剂、凯夫拉纤维、阻燃剂依次加入反应釜，在室温下混合搅拌1～2h，得所述B组分；
c)、将A组分和B组分按照质量份配比1:0.8～1:1.8进行混合，在搅拌速度为600～1800rps下，充分搅拌5～60s后，倒入模具中发泡、熟化，脱模，得所述的凯夫拉纤维-聚氨酯复合发泡材料。
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