Accessible and sustainable Cu(0)-mediated radical polymerisation for the functionalisation of surfaces
Accessible and sustainable Cu(0)-mediated radical polymerisation for the functionalisation of surfaces
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DOI：
10.1039/d0py00516a
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发表时间：
2020-06
影响因子：
4.6
通讯作者：
Oliver Frank Uttley;Leonie Alice Brummitt;S. Worrall;S. Edmondson
中科院分区：
文献类型：
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作者：
Oliver Frank Uttley;Leonie Alice Brummitt;S. Worrall;S. Edmondson
聚合物刷由于其化学和机械鲁棒性以及包括抗菌和抗微生物行为在内的各种有用特性而具有用于功能化表面的巨大潜力。一种这样的感兴趣的接枝聚合物是聚[2-（甲基丙烯酰氧基）乙基]三甲基氯化铵（PMETAC），由于季铵氯化物基团（QAC）的存在，显示出具有优异的抗菌行为。先前的研究已经表明，增加QAC的密度增加了这些表面的功效，因此生产厚的PMETAC刷是非常可取的。Cu（0）介导的自由基聚合（CuRP）为这些表面的生产提供了一种简单的途径。朝着更可持续的化学方向发展的趋势导致了对环境友好溶剂中聚合反应的研究，重点放在可回收和易于获得的催化剂上。在这项研究中，生长的PMETAC刷高达300 nm的干燥厚度（约425 nm的水溶胀厚度）被证明，厚于任何以前的报告，我们发现这种聚合物刷。此外，自来水被用作廉价和容易获得的溶剂，催化剂来自铜线。与常用的CuBr 2催化剂相比，铜线的使用导致更厚的涂层，其也显示出更低的溶胀比，这意味着增加的接枝密度。该方案可以在7天的时间内连续循环而不改变单体溶液或催化剂，其中许多晶片在该时间段内被官能化而接枝量没有显著减少。此外，聚合可以在环境（非惰性）条件下进行，没有脱气步骤，同样对接枝没有显著损害。
Polymer brushes have great potential for use in functionalising surfaces due to their chemical and mechanical robustness, and wide variety of useful properties including antibacterial and antifouling behaviour. One such grafted polymer of interest is poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride (PMETAC), shown to have excellent antibacterial behaviour due to the presence of quaternary ammonium chloride groups (QACs). Previous studies have shown that increasing the density of QACs increases the efficacy of these surfaces, therefore the production of thick PMETAC brushes is highly desirable. Cu(0)-mediated radical polymerisation (CuRP) offers a simple route to the production of these surfaces. A movement towards more sustainable chemistry has led to research into polymerisations in environmentally benign solvent, with focus placed on recycled and easily accessible catalysts. In this study, the growth of PMETAC brushes up to 300 nm dry thickness (∼ 425 nm water-swollen thickness) is demonstrated, thicker than any previous report we have found for this polymer brush. Furthermore, tap water is used as a cheap and readily available solvent, with a catalyst derived from copper wire. The use of copper wire, compared to the commonly used CuBr2 catalyst, leads to thicker coatings which also display a lower swelling ratio, implying an increased grafting density. The protocol can be continuously cycled over a 7-day period without changing the monomer solution or catalyst, with numerous wafers being functionalised over the time period with no significant reduction in grafted amount. In addition, the polymerisation can be carried out in ambient (non-inert) conditions with no degassing steps, again without with significant detriment to grafting.