近年来，刺激响应聚合物因其独特的性质而受到广泛关注，这类聚合物能够感受外界环境刺激（包括光、电、热、力、氧化还原、pH、化学、环境和生物信号等刺激）而产生响应，从而引起体系物理或化学性质的改变。而梯度聚合物则是伴随着可控自由基聚合技术的诞生、发展而出现和形成的一类新型聚合物，区别于无规和嵌段聚合物，梯度聚合物表现出单体组成沿分子链渐变的性质，其中，由亲水性单元和憎水性单元组成的两亲性梯度聚合物在选择性溶剂中可自组装形成多种聚集体，因此具有多方面的潜在应用价值，比如超分子组装体、智能涂料、网络或这些可能应用的组合。本文调研了有关梯度聚合物方面的研究工作，综述了几种梯度聚合物的合成方法，如活性阴离子聚合法、可控自由基聚合法（包括氮氧稳定自由基聚合、原子转移自由基聚合及可逆加成断裂链转移自由基聚合）和开环聚合法等，同时阐述了梯度聚合物的自组装及刺激响应行为，尤其是其独特的热和pH敏感性。此外，还对由两亲性嵌段聚合物和两亲性梯度聚合物自组装形成的聚集体的刺激响应行为进行了详细地论述和比较，并指出了梯度聚合物的应用前景和发展方向。
Stimuli-responsive polymers have attracted much attention in recent years due to their unique properties. These polymers can respond to a variety of external stimuli, which include optical, electrical, thermal, mechanical, redox, pH, chemical, environmental and biological signals, and cause the change in the physical or chemical properties of the system. Gradient polymers form a new class of materials that come into existence with the advent of living polymerization techniques. Unlike random and block polymers, gradient polymers vary their monomer compositions gradually along molecular chains. Among them, amphiphilic gradient polymers which consist of hydrophilic units and hydrophobic units, can self-assemble to form various aggregates in selective solvents. Amphiphilic gradient polymers reveal many potential applications in different fields, such as supramolecular assemblies, smart coatings, networks or some combination of these possibilities. This article summarizes recent research progress on the synthesis of gradient polymers, such as living anionic polymerizations, controlled/living radical polymerizations (including nitroxide-mediated polymerization, atom transfer radical polymerization and reversible addition-fragmentation chain transfer polymerization) and ring opening polymerizations. The second part discusses their self-assembly and stimuli-responsive behaviors, especially for distinctive thermo-sensitivity and pH-sensitivity. In particular, the divergent stimuli responsive behaviors of aggregates self-assembled from amphiphilic block polymers and amphiphilic gradient polymers are discussed and compared in detail. The development prospect of this research field and its potential applications are discussed as well in the last part.
Contents
1 Introduction
2 Synthesis of gradient polymers
2.1 Living anionic polymerization
2.2 Nitroxide mediated polymerization
2.3 Atom transfer radical polymerization
2.4 Reversible addition-fragmentation chain transfer polymerization
2.5 Cationic ring opening polymerization
2.6 Others
3 Self-assembly methods of gradient polymers
4 Stimuli responsive property of gradient polymer aggregates
4.1 Temperature responsive property of gradient polymer aggregates
4.2 pH responsive property of gradient polymer aggregates
5 Conclusion
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