Syndioselective Polymerization of a BN Aromatic Vinyl Monomer
Syndioselective Polymerization of a BN Aromatic Vinyl Monomer
复制标题
DOI：
10.1021/acs.macromol.8b01707
复制
发表时间：
2018-09-11
期刊：
影响因子：
5.5
通讯作者：
Klausen, Rebekka S.
中科院分区：
文献类型：
--
作者：
Mendis, Shehani N.;Zhou, Tiffany;Klausen, Rebekka S.
引入了一种获得有规立构极性聚烯烃的新合成平台。我们通过单环戊二烯基钛络合物对 BN 2-乙烯基萘 (BN2VN) 的间选择性聚合来展示芳香族氮杂硼烷衍生物的稳定性。均相早期过渡金属催化剂是用于合成高度有规立构间规聚苯乙烯（sPS）的成熟体系，但这些配合物的亲氧性质导致催化剂与极性单体分解。 BN2VN 与配位聚合的相容性以及其拦截苯乙烯聚合机制的能力归因于其芳香性。有机硼烷侧链的立构保留后聚合氧化生成间同立构聚（乙烯醇）（sPVA），这是PBN2VN具有多种后官能化潜力的一个例子。
A new synthetic platform accessing stereoregular polar polyolefins is introduced. We showcase the stability of aromatic azaborine derivatives by demonstrating the syndioselective polymerization of BN 2-vinylnaphthalene (BN2VN) by a monocyclopentadienyl titanium complex. Homogeneous early transition metal catalysts are well-established systems for the synthesis of highly stereoregular syndiotactic polystyrene (sPS), but the oxophilic nature of these complexes results in catalyst decomposition with polar monomers. BN2VN's compatibility with coordination polymerization, and its ability to intercept the mechanism of styrene polymerization, is attributed to its aromaticity. Stereoretentive postpolymerization oxidation of the organoborane side chain generates syndiotactic poly(vinyl alcohol) (sPVA), an example of PBN2VN's potential for diverse postfunctionalization.