CN104945597B - 一种具有阻燃性能的体型交联可修复聚氨酯的合成方法 - Google Patents

一种具有阻燃性能的体型交联可修复聚氨酯的合成方法 Download PDF

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CN104945597B
CN104945597B CN201510339219.9A CN201510339219A CN104945597B CN 104945597 B CN104945597 B CN 104945597B CN 201510339219 A CN201510339219 A CN 201510339219A CN 104945597 B CN104945597 B CN 104945597B
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杜鹏飞
陈登龙
伍毓强
白昕
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Quangang Petrochemical Research Institute of Fujian Normal University
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Abstract

本发明的目的在于提供一种具有阻燃性能的体型交联可修复聚氨酯的合成方法，其特征在于通过9，10‑ 二氢‑9‑ 氧杂‑10‑ 磷杂菲‑10‑ 氧化物(DOPO)直接与过量的4,4'‑双马来酰亚胺基二苯甲烷（BMI）发生亲核加成反应来制备DOPO封端的单马来酰亚胺和未反应的双马来酰亚胺的混合物（平均马来酰亚胺官能度为1.50～1.80），再与多呋喃封端的聚氨酯预聚物发生DA反应将DOPO和DA加成物同时引入到聚氨酯中，本发明制备的新型聚氨酯将DOPO的阻燃性能、DA加成物的修复性能以及聚氨酯的力学性能结合起来，具有很好的应用前景和经济社会效益。

Description

一种具有阻燃性能的体型交联可修复聚氨酯的合成方法
技术领域
本发明属于聚氨酯材料领域，具体涉及一种具有阻燃性能的体型交联可修复聚氨酯的合成方法。
背景技术
通过将呋喃/马来酰亚胺体系的DA加成物引入到聚氨酯中可以使合成的聚氨酯材料具有可修复性能，即聚氨酯材料受到损伤后可以简单地通过加热来实现对材料的修复，降低了聚氨酯材料在使用过程中的安全隐患，延长了聚氨酯材料的使用寿命。
然而，引入呋喃/马来酰亚胺体系的DA加成物后的可修复聚氨酯跟普通的未阻燃的聚氨酯一样容易燃烧，并且燃烧后产生大量的熔滴，极易使火势迅速蔓延。同时，燃烧过程中还会分解产生HCN、CO、NO和NO2等有毒烟雾，极易造成人员窒息死亡，严重危害人身和财产安全。较差的阻燃性能严重限制了可修复聚氨酯在一些需要考虑阻燃性能领域中的应用。因此，在可修复聚氨酯的设计和制备过程中，急切地需要提高其阻燃性能来满足这些应用领域的要求，扩大聚氨酯的应用范围。
普通聚氨酯的阻燃可以分为添加型和反应型两种。其中，反应型聚氨酯阻燃剂作为反应单体参与反应，使得聚氨酯本身含有阻燃成分，因而对材料的性能影响小、稳定性好。中国申请专利103833947A(张杰，付双，徐勉，一种用于聚氨酯的反应型无卤含磷阻燃剂的合成及应用，中国专利，2014-06-04)公开了一种用于聚氨酯的反应型无卤含磷阻燃剂的合成及应用。通过DOPO与不饱和羧酸或酸酐形成含磷单体衍生物，进而与多元醇发生酯化反应形成分子量300~1000g/mol,端基为羟基，官能度为2~6，室温下为液态的反应型无卤含磷阻燃剂。并将其应用在聚氨酯硬泡中，提高了聚氨酯硬泡的阻燃性能。张通等（张通，郑玉婴.合成反应型磷酸酯及其对TPU阻燃和力学性能的影响[J].功能材料，2012，13(43)：1733-1736。）以正丁醇、三氯氧磷和1，4-丁二醇合成了双羟基的液态磷酸酯阻燃剂（BBHP），将其作为扩链剂而引入到聚氨酯弹性体中。关于呋喃/马来酰亚胺DA加成物的可修复聚氨酯的阻燃报道还很少。
9，10- 二氢-9- 氧杂-10- 磷杂菲-10- 氧化物(DOPO)是新型环保型阻燃剂中间体，由DOPO合成的阻燃剂具有高效阻燃性，无烟无毒。由于P-C键的存在，化学稳定好，在提高高分子材料的阻燃性、热稳定性的同时，保持或仅部分改变高分子材料的其他性能。DOPO具有六元磷杂环的结构，如下图所示。DOPO中的P具有孤对电子，易发生亲核加成反应，而且DOPO上的苯环为供电子基团，与相邻的P=O键产生共轭作用，形成一大π键，使得P原子上的电子云密度增加。因此，P-H键上的H原子极其活泼而容易失去，P原子成为P（δ-）而容易与正离子发生亲核加成反应。而4,4'-双马来酰亚胺基二苯甲烷（BMI）中存在两个马来酰亚胺基团，马来酰亚胺中的两个羰基的强吸电子效应使得双键上C原子的电子云密度降低形成碳正离子，容易发生亲电加成反应。
本发明利用DOPO与过量的BMI（摩尔比=1:3～10）发生亲核加成反应而制备DOPO封端的单马来酰亚胺和未反应的双马来酰亚胺的混合物（平均马来酰亚胺官能度为1.50~1.80）。然后再与聚合MDI制备的多呋喃环封端的聚氨酯预聚物发生DA反应，将DOPO和DA加成物同时引入到聚氨酯中。本发明制备的新型聚氨酯将DOPO的阻燃性能、DA加成物的修复性能以及聚氨酯的力学性能结合起来，具有很好的应用前景和经济社会效益。
发明内容
本发明公开了一种具有阻燃性能的体型交联可修复聚氨酯的合成方法，本发明是通过DOPO与过量的BMI发生亲核加成反应来制备平均官能度为1.67~1.90的亲二烯体，再与二烯体（多呋喃封端的聚氨酯预聚物，平均官能度为3.4）发生DA反应，将阻燃剂DOPO和DA加成物同时引入聚氨酯材料中。与BMI (平均官能度为2）相比，本发明合成的亲二烯体的平均官能度略有降低，有利于降低聚氨酯材料的交联度而改善聚氨酯材料因交联度过大所导致的材料变硬、断裂伸长率降低、力学性能降低，本发明最终实现了聚氨酯材料可修复性能和阻燃性能的完美结合，合成方法简单方便，具有显著的经济和社会效益。
本发明的技术方案所采取的具体步骤如下：
1）呋喃基聚氨酯预聚物的合成：
真空除水后100份重量PBA-1000，加入54.3~90.5份重量的聚合MDI，加入155~191份重量的DMF，体系浓度为50wt%, 60℃反应2~3h后，冰水浴下加入20.5~47.5份重量的糠胺（糠胺溶解于21~48份重量的DMF中），30分钟内加完，冰水浴反应2小时后在室温下反应0.5~1h。
2）含DOPO基的BMI的合成：
50~106份BMI先溶解于50~106份重量DMF中，再将17.3~25.6份DOPO溶解于17.3~25.6份DMF中并缓慢滴加到BMI的DMF溶液中（1小时内滴加完毕），在N2条件下80~90℃反应2~3小时。
3）含DOPO的DA加成物的合成：
将上述两溶液体系混合后在60℃下反应0.5~2h，即可倒入聚四氟乙烯盘中，并放入鼓风烘箱中干燥成膜。
本发明的优点在于：１.合成方法简单方便；２. DOPO的引入给可修复聚氨酯带来阻燃性能。3.DOPO的引入适当地降低了可修复聚氨酯的的交联度，提高了聚氨酯材料的断裂伸长率。
本发明最终实现了阻燃性能、可修复性能和力学性能的完美结合。
具体实施方式
以下是本发明的几个具体实施例，但是本发明不仅限于此。
实施案例1.
1）呋喃基聚氨酯预聚物的合成
真空除水后100份重量PBA-1000，加入72.4份重量的聚合MDI，加入173份重量的DMF，N2条件下，先在 60℃反应2~3h，然后在冰水浴下加入34份重量的糠胺（糠胺溶解于34份重量的DMF中），30分钟内加完，冰水浴反应2小时后在室温下反应0.5~1h。
2）含DOPO基的BMI的合成
78份BMI先溶解于81份重量DMF中，再将20份DOPO溶解于20份DMF中并缓慢滴加到BMI的DMF溶液中（1小时内滴加完毕），在N2条件下80~90℃反应2~3小时。
3）含DOPO的DA加成物的合成
将上述两溶液体系混合后在N2氛围、60℃下反应1~2h，即可倒入聚四氟乙烯盘中，并放入鼓风烘箱中干燥成膜。
经测试：最终的聚氨酯产物的极限氧指数可以达到26，修复效率可以达到８０％以上，与未引入DOPO阻燃剂的可修复聚氨酯大体相当。其断裂拉伸强度可以达到３0 MPa，与未引入DOPO阻燃剂的可修复聚氨酯拉伸强度相当，而断裂伸长率却从190％提高到了220％。
实施案例2
1）呋喃基聚氨酯预聚物的合成
真空除水后100份重量PBA-1000，加入91份重量的聚合MDI，加入191份重量的DMF，N2条件下，先在 60℃反应2~3h，然后在冰水浴下加入48份重量的糠胺（糠胺溶解于48份重量的DMF中），30分钟内加完，冰水浴反应2小时后在室温下反应0.5~1h。
2）含DOPO基的BMI的合成
106份BMI先溶解于106份重量DMF中，再将26份DOPO溶解于26份DMF中并缓慢滴加到BMI的DMF溶液中（1小时内滴加完毕），在N2条件下80~90℃反应2~3小时。
3）含DOPO的DA加成物的合成
将上述两溶液体系混合后在60℃下反应0.5~1h，即可倒入聚四氟乙烯盘中，并放入鼓风烘箱中干燥成膜。
经测试：最终的聚氨酯产物的极限氧指数可以达到28，修复效率可以达到８０％以上，与未引入DOPO体系的可修复聚氨酯大体相当。其断裂拉伸强度可以达到40 MPa，与未引入DOPO可修复聚氨酯的拉伸强度相当，而断裂伸长率却从150％提高到了170％。

Claims (3)

1.一种具有阻燃性能的体型交联可修复聚氨酯的合成方法，其合成方法包括以下几个步骤：
1）呋喃基聚氨酯预聚物的合成：
真空除水后100份重量PBA-1000，加入54.3~90.5份重量的聚合MDI，加入155~191份重量的DMF，体系浓度为50wt%, 60℃反应2~3h后，冰水浴下加入20.5~47.5份重量的糠胺，其中糠胺应预先溶解于21~48份重量的DMF中的，30分钟内加完，冰水浴反应2小时后在室温下反应0.5~1h；
2）DOPO-BMI的合成：
50~106份BMI先溶解于50~106份重量DMF中，再将17.3~25.6份DOPO溶解于17.3~25.6份DMF中并缓慢滴加到BMI的DMF溶液中，在1小时内滴加完毕，在N2条件下80~90℃反应2~3小时；
3）含DOPO和DA加成物的聚氨酯的合成：
将上述两溶液体系混合后在60℃下反应0.5~2h，即可倒入聚四氟乙烯盘中，并放入鼓风烘箱中干燥成膜；
通过两组分发生DA反应而制得：
a)多呋喃环封端的聚氨酯预聚物；
b）DOPO与大大过量的BMI发生亲核加成反应制备的DOPO封端的单马来酰亚胺和未反应的双马来酰亚胺的混合物，其平均马来酰亚胺官能度为1.50~1.80。
2.根据权利要求1所述的一种具有阻燃性能的体型交联可修复聚氨酯的合成方法，其特征在于所述的呋喃基聚氨酯预聚物由聚合MDI与聚酯多元醇PBA-1000按照NCO:OH=4.05~6.75:2先制备多异氰酸酯封端的聚氨酯预聚物，再与糠胺反应来制备多呋喃环封端的聚氨酯预聚物。
3.根据权利要求1所述的一种具有阻燃性能的体型交联可修复聚氨酯的合成方法，其特征在于所述的含DOPO基BMI的合成是将DOPO加入到过量的BMI中，DOPO与BMI的摩尔比为1:2~5、反应温度为80~90℃、反应溶剂为DMF、反应时间为2~3h。
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