Synthesis of discrete bottlebrush polymers via the iterative convergent growth technique and post-functionalization,Polymer Chemistry

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Synthesis of discrete bottlebrush polymers via the iterative convergent growth technique and post-functionalization
Polymer Chemistry ( IF 4.1 ) Pub Date : 2022-05-27 , DOI: 10.1039/d2py00573e
Hyunji Ma ₁ , Sungmin Ha ₁ , Jisu Jeong ₁ , Valene Wang ₁ , Kyoung Taek Kim ₁

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Bottlebrush polymers (BBPs) have unique physical properties that arise from polymeric side chains that are densely grafted onto their polymer backbone. Despite their promising attributes, well-defined BBPs are challenging to prepare partly due to steric hindrance encountered during macromonomer polymerization or during the coupling of side-chain polymers with functional groups present in the repeating units of the backbone polymers. Here we report the synthesis of perfectly discrete BBPs with absolutely defined chemical structures. The copolyester backbone, composed of up to 64 repeating units of an alternating sequence of lactic acid and 2-hydroxy-4-pentenoic acid, was synthesized using an iterative convergent growth technique. Discrete side chains, such as discrete polylactides (LA_n-SH), were introduced in the presence of the vinyl groups of the 2-hydroxy-4-pentenoic acid residues on the copolyester backbone using thiol–ene click chemistry promoted by UV light (λ = 365 nm), which produced a fully grafted BBP, t-LP(LA₈)32-LA₈ (Molecular weight (MW = 34 kDa). We also synthesized an amphiphilic bottlebrush block copolymer (BBCP) (MW = 19 kDa) by introducing the hydrophobic dodecanethiol and discrete poly(ethylene glycol) as side chains. The resulting BBCP self-assembled into well-defined micelles in water. Discrete BBCPs may serve as model systems that help to elucidate the role of the branched architecture on the physical and chemical behavior of BBCPs in bulk and solution.

中文翻译：

通过迭代收敛生长技术和后功能化合成离散瓶刷聚合物

瓶刷聚合物 (BBP) 具有独特的物理特性，这些特性源于密集接枝到其聚合物主链上的聚合物侧链。尽管具有良好的特性，但定义明确的 BBP 难以制备，部分原因是在大分子单体聚合过程中或在侧链聚合物与主链聚合物重复单元中存在的官能团偶联过程中遇到空间位阻。在这里，我们报告了具有绝对定义的化学结构的完美离散 BBP 的合成。共聚酯骨架由多达 64 个交替序列的乳酸和 2-羟基-4-戊烯酸的重复单元组成，是使用迭代收敛生长技术合成的。离散侧链，例如离散聚丙交酯 (LA _n-SH)，在共聚酯主链上存在 2-羟基-4-戊烯酸残基的乙烯基的情况下，使用紫外光 ( λ = 365 nm) 促进的硫醇-烯点击化学引入，产生完全接枝的BBP, t-LP(LA ₈ )32-LA ₈ (分子量 (MW = 34 kDa)。我们还通过引入疏水性十二烷硫醇和离散的聚 (乙烯) 合成了一种两亲瓶刷嵌段共聚物 (BBCP) (MW = 19 kDa)乙二醇）作为侧链。由此产生的 BBCP 在水中自组装成定义明确的胶束。离散的 BBCP 可以作为模型系统，帮助阐明支链结构对 BBCP 在本体和溶液中的物理和化学行为的作用。

更新日期：2022-06-01

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