An Organoborane Vinyl Monomer with Styrene-like Radical Reactivity: Reactivity Ratios and Role of Aromaticity
An Organoborane Vinyl Monomer with Styrene-like Radical Reactivity: Reactivity Ratios and Role of Aromaticity
复制标题
DOI：
10.1021/acs.macromol.8b01368
复制
发表时间：
2018-08
期刊：
影响因子：
5.5
通讯作者：
H. L. van de Wouw;Elorm C Awuyah;Jodie I. Baris;R. Klausen
中科院分区：
文献类型：
--
作者：
H. L. van de Wouw;Elorm C Awuyah;Jodie I. Baris;R. Klausen
BN 2-乙烯基萘 (BN2VN) 是一种通过氢过氧化钠氧化生产乙烯醇共聚物的新型前体。我们证明了 BN 杂环的不寻常芳香性导致了类似苯乙烯的反应性。包括结构参数和核无关化学位移 (NICS) 值在内的计算数据支持 BN2VN 的 BN 萘侧链的芳香性。苯乙烯 (St) 和 BN2VN 反应性比 (r1(BN2VN) = 0.423；r2(St) = 2.30；r1r2 = 0.97）通过非线性最小二乘 (NLLS) 统计方法确定。我们展示了对共聚物物理性能的控制，包括玻璃化转变温度。这项工作概述了合成定制聚合苯乙烯-乙烯醇结构的设计原则。
BN 2-vinylnaphthalene (BN2VN) is a novel precursor to vinyl alcohol copolymers via sodium hydroperoxide oxidation. We show that the unusual aromaticity of the BN heterocycle leads to styrene-like reactivity. Computational data including structural parameters and nucleus independent chemical shift (NICS) values support the aromaticity of the BN naphthalene side chain of BN2VN. Styrene (St) and BN2VN reactivity ratios (r1(BN2VN) = 0.423; r2(St) = 2.30; r1r2 = 0.97) were determined by nonlinear least-squares (NLLS) statistical methods. We demonstrate control of copolymer physical properties, including glass transition temperature. This work outlines design principles for the synthesis of tailored polymeric styrene–vinyl alcohol architectures.