RAFT Polymerization of an Aromatic Organoborane for Block Copolymer Synthesis
RAFT Polymerization of an Aromatic Organoborane for Block Copolymer Synthesis
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用于嵌段共聚物合成的芳香族有机硼烷的 RAFT 聚合
DOI：
10.1039/d3py00706e
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发表时间：
2023
影响因子：
4.6
通讯作者：
Klausen, Rebekka S
中科院分区：
文献类型：
--
作者：
Melvin, Sophia J.;Mediavilla, Braden A.;Ambrosius, Em G.;Jiang, Qifeng;Fang, Fan;Ji, Yuyang;Mukhopadhyaya, Tushita;Katz, Howard E;Klausen, Rebekka S
聚乙烯醇（PVA）的传统前驱体醋酸乙烯酯（VAc）的可控自由基聚合反应是合成聚苯乙烯-嵌段-聚乙烯醇（PS-b-PVA）的一个难点。我们报告的合成和表征的PS-b-PVA嵌段共聚物（BCP）的可定制的PVA嵌段长度通过RAFT聚合的替代前体，一种芳香族有机硼烷共聚单体BN 2-乙烯基萘（BN 2 VN）。描述了使用2-氰基-2-丙基十二烷基三硫代碳酸酯（CPDT）的BN 2 VN（RB）的RAFT均聚。固体NMR、ATR-IR、SEC和热重分析表明PS-b-PVA和RS-b-RB之间存在显著差异。研究了在C-B侧链氧化转化为C-OH侧链期间三硫代碳酸酯端基的命运;而水合醛（例如，gem-二醇），但没有发现确凿的证据。
Synthesizing polystyrene-block-poly(vinyl alcohol) (PS-b-PVA) via controlled radical polymerization of vinyl acetate, the traditional precursor to polyvinyl alcohol (PVA), is challenging due to the reactivity of the unconjugated α-acetoxy radical. We report the synthesis and characterization of PS-b-PVA block copolymers (BCPs) with tailorable PVA block lengths via RAFT polymerization of an alternative precursor, an aromatic organoborane comonomer BN 2-vinylnapthalene (BN2VN). RAFT homopolymerization of BN2VN (RB) using 2-cyano-2-propyl dodecyl trithiocarbonate (CPDT) is described. Solid-state NMR, ATR-IR, SEC and thermogravimetric analysis reveal significant differences between PS-b-PVA and RS-b-RB. The fate of the trithiocarbonate end-group during oxidative conversion of the C–B side chain to a C–OH side chain was studied; while a hydrated aldehyde (e.g., gem-diol) was hypothesized, conclusive evidence was not found.