Tailoring polymer dispersity by mixing chain transfer agents in PET-RAFT polymerization,Polymer Chemistry

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Tailoring polymer dispersity by mixing chain transfer agents in PET-RAFT polymerization
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-07-15 , DOI: 10.1039/d0py00823k
Kostas Parkatzidis _{1,

2,

3,

4} , Nghia P. Truong _{1,

2,

3,

4} , Maria Nefeli Antonopoulou _{1,

2,

3,

4} , Richard Whitfield _{1,

2,

3,

4} , Dominik Konkolewicz _{5,

6,

7,

8} , Athina Anastasaki _{1,

2,

3,

4}

Affiliation

Here we report a simple and versatile batch methodology to tailor polymer dispersity utilizing PET-RAFT polymerization. By mixing two chain transfer agents (CTAs) possessing different transfer constants (a higher and a lower transfer constant CTA) in different ratios, control over the dispersity (Đ = 1.08–1.82) can be achieved for a range of monomer classes including methacrylates, acrylates and acrylamides while maintaining monomodal molecular weight distribution. The high end-group fidelity of both low and high dispersity macroCTAs was confirmed by the synthesis of block copolymers. In contrast to previously developed photo-mediated methodologies, we show that PET-RAFT exhibits perfect temporal control for all targeted dispersities regardless of the percentage of the lower transfer constant CTA employed. Other benefits of the approach include the use of visible light irradiation, ppm concentrations of a photo-redox catalyst and the possibility to manipulate Đ in the absence of external deoxygenation methodologies, which significantly simplify the process.

中文翻译：

通过在PET-RAFT聚合中混合链转移剂来调整聚合物的分散性

在这里，我们报告了一种简单且通用的批处理方法，以利用PET-RAFT聚合来定制聚合物的分散性。通过将两种具有不同转移常数（较高和较低转移常数CTA）的链转移剂（CTA）以不同的比例混合，可以控制分散度（Đ= 1.08–1.82）对于一系列单体类别（包括甲基丙烯酸酯，丙烯酸酯和丙烯酰胺）可以实现，同时保持单峰分子量分布。嵌段共聚物的合成证实了低和高分散度macroCTA的高端基保真度。与以前开发的光介导方法相反，我们显示PET-RAFT对所有目标分散性均表现出完美的时间控制，而与所采用的较低转移常数CTA的百分比无关。该方法的其他好处包括使用可见光辐照，光氧化还原催化剂的ppm浓度以及在没有外部脱氧方法的情况下操作Đ的可能性，这大大简化了过程。

更新日期：2020-08-11

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