Facile topological transformation of ABA triblock copolymers into multisite, single-chain-folding and branched multiblock copolymers via sequential click coupling and anthracene chemistry,Polymer Chemistry

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Facile topological transformation of ABA triblock copolymers into multisite, single-chain-folding and branched multiblock copolymers via sequential click coupling and anthracene chemistry
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-1-13 , DOI: 10.1039/d0py01649g
Yanzhe He _{1,

2,

3,

4,

5} , Zhigang Wang _{1,

2,

3,

4,

5} , Peng Liu _{1,

2,

3,

4,

5} , Xiangdong Zhou _{5,

6,

7,

8} , Youliang Zhao _{1,

2,

3,

4,

5}

Affiliation

Architecture-transformable polymers with rational rearrangement of the chain structure may reshape the future of smart materials. Although the transition from block to multisegmented block copolymers is well documented, further transformation into high-order architectures has been scarcely revealed. This research aims at reaction-induced sequential transitions from ABA triblock copolymers (TBPs) to multisite (MMPs), single-chain-folding (SMPs) and branched (BMPs) multiblock copolymers. Consecutive ATRP and azidation afford α,ω-azido-mid-anthryl-functionalized ABA (A = poly(tert-butyl acrylate), B = polystyrene) copolymers, the double-strain-promoted azide−alkyne cycloaddition reaction gives (ABA)_n-type MMPs, and UV-induced dimerization of pendant anthryl groups is adopted to generate SMPs or BMPs. The utilization of the self-accelerating click reaction and anthracene chemistry allows efficient construction of the desired polymers in a few hours, affording a robust platform for fast formation and transformation of MMPs. Fractional precipitation endows MMPs with relatively low dispersity and weight-average polymerization degree of ABA (n_w) up to 72. With the formation of a more compact structure, the single-chain folding is prone to result in reduced apparent molar mass relying on dispersity and n_w as well as decreased solution viscosity. The success of this study paves the way for on-demand transformation and tunable properties of multisegmented macromolecular architectures.

中文翻译：

通过顺序点击偶联和蒽化学，轻松地将ABA三嵌段共聚物拓扑转化为多位，单链折叠和支化的多嵌段共聚物

具有链结构合理重排的可转换结构的聚合物可能会重塑智能材料的未来。尽管已经很好地证明了从嵌段到多链段嵌段共聚物的转变，但是几乎没有揭示出进一步转变成高阶结构。这项研究的目标是反应诱导的从ABA三嵌段共聚物（TBP）到多位点（MMP），单链折叠（SMP）和支链（BMP）的多嵌段共聚物的顺序过渡。连续进行ATRP和叠氮化可得到α，ω-叠氮基-仲-蒽官能化的ABA（A =聚（丙烯酸叔丁酯），B =聚苯乙烯）共聚物，双应变促进的叠氮化物-炔烃环加成反应得到（ABA）_n型MMP，以及UV诱导的蒽基侧基的二聚化生成SMP或BMP。利用自加速点击反应和蒽化学，可以在数小时内有效构建所需的聚合物，从而为快速形成和转化MMP提供了强大的平台。分级沉淀使MMP具有相对较低的分散度，ABA（n _w）的重均聚合度高达72。随着形成更致密的结构，单链折叠容易导致依赖于分散度的表观摩尔质量降低和n _w以及降低溶液粘度。这项研究的成功为多片段大分子体系结构的按需转化和可调特性铺平了道路。

更新日期：2021-01-13

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