Facile synthesis of branched polyvinyl acetate via redox-initiated radical polymerization†,Polymer Chemistry

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Facile synthesis of branched polyvinyl acetate via redox-initiated radical polymerization†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-05-09 00:00:00 , DOI: 10.1039/c8py00286j
Ni Zeng _{1,

2,

3,

4} , Yuyan Yu _{1,

2,

3,

4} , Junbing Chen _{1,

2,

3,

4} , Xiao Meng _{1,

2,

3,

4} , Leilei Peng _{1,

2,

3,

4} , Yi Dan _{1,

2,

3,

4} , Long Jiang _{1,

2,

3,

4}

Affiliation

Although branched polymers find widespread applications, the rational design and synthesis of branched vinyl polymers via the conventional radical (co)polymerization of commercially available monomers is still a challenge for researchers in this field. Using branched polyvinyl acetate (PVAc) as a proof-of-concept, we report a facile approach to synthesize branched polymers via redox-initiated radical copolymerization. In this case, the commercially available monomer 2-(dimethylamino)ethyl methacrylate (DMAEMA), containing both a vinyl group and an initiator fragment (tertiary amine group), serves as an inimer in the presence of an oxidant to copolymerize with vinyl acetate (VAc), leading to the formation of branching architectures. The copolymerization kinetics investigation as well as electron paramagnetic resonance (EPR) measurements were conducted to reveal the reactivity of DMAEMA and the development of branching architectures, while TD-SEC and ¹H-NMR were employed to study the structures of the resulted polymers. The results confirm that DMAEMA can serve as an inimer for the preparation of branched PVAc. Moreover, balancing the feed ratio of DMAEMA to VAc enables the fine control of branching degree. Within our experimental design, a high feed ratio of DMAEMA to VAc leads to high branching, as demonstrated by the Zimm branching factor, g′. This novel methodology involves only commercially available monomers and conventional radical polymerization and hence offers a promising future for preparing branched vinyl polymers on a large scale and at low cost.

中文翻译：

通过氧化还原引发的自由基聚合轻松合成支链聚乙酸乙烯酯†

尽管支链聚合物得到了广泛的应用，但是通过商业上可利用的单体的常规自由基（共）聚合来合理设计和合成支链乙烯基聚合物仍然是该领域研究人员的挑战。使用支化聚乙酸乙烯酯（PVAc）作为概念证明，我们报告了一种通过以下方法合成支化聚合物的简便方法氧化还原引发的自由基共聚。在这种情况下，同时含有乙烯基和引发剂片段（叔胺基）的可商购获得的甲基丙烯酸2-（二甲基氨基）乙酯（DMAEMA）在氧化剂的存在下充当着与乙酸乙烯酯共聚的目标（ VAc），导致分支架构的形成。进行了共聚动力学研究以及电子顺磁共振（EPR）测量，以揭示DMAEMA的反应性和分支结构的发展，而TD-SEC和¹1 H-NMR用于研究所得聚合物的结构。结果证实，DMAEMA可以用作制备支链PVAc的工具。此外，通过平衡DMAEMA与VAc的进料比，可以很好地控制支化度。在我们的实验设计中，如Zimm支化因子g ′所示，DMAEMA与VAc的高进料比导致高支化。这种新颖的方法仅涉及可商购的单体和常规的自由基聚合，因此为大规模和低成本制备支链乙烯基聚合物提供了广阔的前景。

更新日期：2018-05-09

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