【作者】 朱路；

【导师】 唐小真；

【作者基本信息】 上海交通大学 ， 材料学， 2007， 博士

【摘要】 研究提出了一种全新的制备聚合物纳米管的原位模板法,并通过此方法制备了环交联型聚(环三膦腈-co-4,4’-二羟基二苯砜)[poly(cyclotriphosphazene-co-4,4’-sulfonyldiphonel), PZS]纳米管。原位模板法是利用六氯环三膦腈(HCCP)与4,4’-二羟基二苯砜(BPS)在交联缩合反应中原位产生的三乙胺盐酸盐(TEACl)晶体为模板,在超声振荡作用下用一步反应制得PZS纳米管。制备和后处理过程简单,易于工业化生产。核磁跟踪测试表明,HCCP和BPS进行的是双分子亲核取代反应(S_N2),三乙胺(TEA)在反应中不仅作为缚酸剂,而且还起着活化BPS、促进亲核进攻的作用。通过改变反应条件可以控制PZS纳米管的内径在5-10 nm或10-20 nm,长度在1-2μm或者5μm以上,以及PZS纳米管的端口的开口或者闭口结构。PZS纳米管是高度交联的环交联型分子结构。TEM分析证实了PZS纳米管形成过程:随着反应的进行,高度交联的PZS和TEACl晶体从反应溶液中析出,析出的PZS纳米颗粒粘附在TEACl纳米微晶的表面形成核壳结构,最后水洗除去模板TEACl晶体获得PZS纳米管。通过薄层毛细渗透技术测量了PZS纳米管和TEACl微晶体的表面能,运用联立粘合理论进行计算,结果表明PZS能够很好的浸润TEACl晶体,PZS能够在TEACl晶体上自发铺展,粘附功高达88.33 mJ/m~2,是管状纳米结构形成的原始推动力。PZS纳米管具有优异的热稳定性,N2下热分解温度达550 oC,加热至900 oC时仍有55更多还原

【Abstract】 A novel in situ template approach to polymer nanotubes was developed, via which cyclomatrix-type poly(cyclotriphosphazene-co-4,4’-sulfonyldiphonel) (PZS) nanotubes were prepared. Under ultrasonic condition, triethylammonium chloride (TEACl) crystals were formed to act as in situ templates during the polycondensation between hexachlorocyclotriphosphazene (HCCP) and 4,4’-sulfonyldiphenol (BPS). The preparation of PZS nanotubes was simple and easy to scale up, so did the post treatment. 1H NMR monitor of the polycondensation showed that TEA acted as not only acid-acceptor but also catalyst to activate BPS for nucleophilic substitution. And condensation between HCCP and BPS followed a bimolecular nucleophilic substitution (S_N2) pattern. The dimensions of PZS nanotubes could be controlled in a diameter range of 5-10 nm or 10-20 nm, lengths of 1-2μm or more than 5μm, tips of open-ends and close-ends by varying reaction conditions. PZS nanotubes had a molecular structure of highly cross-linked cyclo-matrix.TEM analysis confirmed the formation process of PZS nanotubes: during the polycondensation, highly cross-linked PZS nano-particles and TEACl nano-crystals were first precipitated out of the reaction medium, PZS nano-particles then adhered onto the surfaces of TEACl nano-crystals to form core-shell structures, finally, after removal of the TEACl templates更多还原