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官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能

张方 ,  张航天 ,  杨甜 ,  孔波 ,  郭安儒 ,  章琦 ,  吴一弦

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引用本文: 张方, 张航天, 杨甜, 孔波, 郭安儒, 章琦, 吴一弦. 官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能[J]. 高分子学报, 2020, 51(1): 98-116. doi: 10.11777/j.issn1000-3304.2020.19151 shu
Citation:  Fang Zhang, Hang-tian Zhang, Tian Yang, Bo Kong, An-ru Guo, Qi Zhang, Yi-xian Wu. Synthesis and Property of Novel Functionalized Polytetrahydrofuran-b-polyisobutylene-b-polytetrahydrofuran Triblock Copolymers[J]. Acta Polymerica Sinica, 2020, 51(1): 98-116. doi: 10.11777/j.issn1000-3304.2020.19151 shu

官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃三嵌段共聚物的合成与性能

  • 北京化工大学 化工资源有效利用国家重点实验室 生物医用材料北京实验室　北京 100029

    • 通讯作者: E-mail: wuyx@mail.buct.edu.cn
摘要: 采用2-氯-2,4,4-三甲基戊烷或对二枯基氯为引发剂和TiCl4或FeCl3为共引发剂，引发异丁烯(IB)可控/活性正离子聚合与官能端基转化，设计合成不同分子量及窄分子量分布的端基官能化聚异丁烯，如双端烯丙基溴官能化聚异丁烯(Br-PIB-Br)或双端烯丙基胺官能化聚异丁烯(H2N-PIB-NH2). 采用烯丙基溴/高氯酸银体系引发四氢呋喃(THF)开环聚合，合成聚四氢呋喃活性链(PTHF+). 进一步通过将IB可控/活性正离子聚合与THF可控/活性正离子开环聚合2种方法相结合，设计合成2种新型官能化聚四氢呋喃-b-聚异丁烯-b-聚四氢呋喃(PTHF-b-PIB-b-PTHF)三嵌段共聚物：(1)以上述Br-PIB-Br为大分子引发剂，在AgClO4作用下引发THF活性正离子开环聚合，采用水终止活性链端，设计合成双端为羟基的HO-PTHF-b-PIB-b-PTHF-OH三嵌段共聚物(简称：FIBF-OH)；(2)以上述合成的PTHF+活性链与H2N-PIB-NH2链端胺基发生高效亲核取代反应，设计合成中间链段连接点含―NH―官能基团的PTHF-b-HN-PIB-NH-b-PTHF三嵌段共聚物(简称：FIBF-NH). 在上述三嵌段共聚物中，极性PTHF链段与非极性PIB链段的热力学不相容，导致其呈现明显的微相分离，且微观形态与共聚组成相关. PTHF均聚物易结晶，在上述共聚物中由于PTHF链段单端受限致其结晶性减弱. 三嵌段共聚物分子链的中间连接点含―NH―官能基团，具有更强的氢键作用，促进PTHF链段重排并结晶，易形成更紧密的超分子网络结构，导致即使在PTHF链段相对分子量为0.7 kg·mol−1时仍具有较强的结晶性，且结晶熔融温度明显提高. 此外，由于FIBF-NH中形成超分子网络结构，使材料具有优异的自修复性能，材料表面的切痕在常温下10 min 后可以完全自愈合. 本文设计合成的新型官能化PTHF-b-PIB-b-PTHF三嵌段共聚物兼具有PTHF与PIB的优良性能，在生物医用、智能修复等功能材料领域具有潜在的应用前景.

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  • 发布日期:  2020-01-01
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