Accessing new and scalable high molecular weight branched copolymer structures using transfer-dominated branching radical telomerisation (TBRT)
Accessing new and scalable high molecular weight branched copolymer structures using transfer-dominated branching radical telomerisation (TBRT)
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DOI：
10.1039/d2py00174h
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发表时间：
2022-03-30
影响因子：
4.6
通讯作者：
Rannard, Steve P.
中科院分区：
文献类型：
--
作者：
Cassin, Savannah R.;Flynn, Sean;Rannard, Steve P.
学术上和商业上支化聚合物的合成通常依赖于由单一单体衍生的重复化学。支化均聚物的文献报道往往依赖于难以规模化的化学物质。分步生长聚合被广泛使用，这也限制了得到的支化大分子的相对分子质量。最近关于转移主导型支化自由基端粒化(TBRT)的报道提供了通向一系列以前无法利用的大分子结构的路线，这些大分子结构利用自由基反应但导致阶梯状生长的骨架。在这里，我们展示了如何通过三种新的合成策略，通过三种新的合成策略，利用简单的自由基反应条件，使用TBRT来形成具有阶跃生长主干化学成分的支化统计共聚物，从而产生具有容易调节的物理性能的新材料。从概念上概述了这些策略，并以实验实例为例，玻璃化转变温度的测定为均相统计共聚的形成提供了明确的证据。
Academic and commercial branched polymer synthesis very commonly relies upon a repeating chemistry derived from a single monomer. Literature reports of branched homopolymers often rely upon chemistries that are difficult to scale. Step-growth polymerisations are widely utilised which also limit the molecular weight of resulting branched macromolecules. The recent reports of Transfer-dominated Branching Radical Telomerisation (TBRT) provide readily accessible routes to a range of previously inaccessible macromolecular architectures utilising free radical reactions but resulting in step-growth-like backbones. Here we show how TBRT may be used to form branched statistical copolymers with step-growth backbone chemistries using facile free radical reaction conditions through three novel synthesis strategies leading to new materials with readily tunable physical properties. The strategies are outlined conceptually, exemplified by experimental examples and determination of glass transition temperatures provides clear evidence of homogeneous statistical copolymer formation.