B(C6F5)3-Catalyzed Group Transfer Polymerization of N,N-Disubstituted Acrylamide Using Hydrosilane: Effect of Hydrosilane and Monomer Structures, Polymerization Mechanism, and Synthesis of α-End-Functionalized Polyacrylamides,Macromolecules

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B(C6F5)3-Catalyzed Group Transfer Polymerization of N,N-Disubstituted Acrylamide Using Hydrosilane: Effect of Hydrosilane and Monomer Structures, Polymerization Mechanism, and Synthesis of α-End-Functionalized Polyacrylamides
Macromolecules ( IF 5.1 ) Pub Date : 2016-04-04 00:00:00 , DOI: 10.1021/acs.macromol.6b00190
Seiya Kikuchi ₁ , Yougen Chen _{2,

3} , Kodai Kitano ₁ , Shin-ichiro Sato ₄ , Toshifumi Satoh ₄ , Toyoji Kakuchi _{2,

4,

5}

Affiliation

The tris(pentafluorophenyl)borane- (B(C₆F₅)₃-) catalyzed group transfer polymerization (GTP) of N,N-disubstituted acrylamide (DAAm) using a moisture-tolerant hydrosilane (HSi) as part of the initiator has been intensively investigated in this study. The screening experiment using various HSis suggested that dimethylethylsilane (Me₂EtSiH) with the least steric bulkiness was the most appropriate reagent for the polymerization control. The chemical structure of the DAAms significantly affected the livingness of the polymerization. For instance, the polymerization of N,N-diethylacrylamide (DEtAAm) using Me₂EtSiH only showed better control over the molecular weight distribution, while that of N-acryloylmorpholine (MorAAm) with a more obstructive side group using the same HSi afforded precise control of the molecular weight as well as its distribution. Given that the entire polymerization was composed of the monomer activation, the in situ formation of a silyl ketene aminal as the true initiator by the 1,4-hydrosilylation of DAAm, and the GTP process, the polymerization mechanism was discussed in detail for each specific case, e.g., the B(C₆F₅)₃-catalyzed polymerizations of DEtAAm and MorAAm and the polymerization of MorAAm using B(C₆F₅)₃ and Me₃SiNTf₂ as a double catalytic system. Finally, the convenient α-end-functionalization of poly(N,N-disubstituted acrylamide) (PDAAm) was achieved by the in situ preparation of functional silyl ketene aminals through the 1,4-hydrosilylation of functional methacrylamides, which has no polymerization reactivity in the Lewis acid-catalyzed GTP, followed by the Me₃SiNTf₂-catalyzed GTP of DAAms.

中文翻译：

使用氢化硅烷的B（C ₆ F ₅）_3-催化的N，N-二取代的丙烯酰胺基团转移聚合：氢化硅烷和单体结构的影响，聚合机理以及α-末端官能化聚丙烯酰胺的合成

N，N-二取代丙烯酰胺（DAAm）的三（五氟苯基）硼烷-（B（C ₆ F ₅）_3-）催化的基团转移聚合（GTP），使用耐湿氢硅烷（H Si）作为引发剂的一部分在这项研究中已进行了深入研究。使用各种H Si的筛选实验表明，具有最小空间体积的二甲基乙基硅烷（Me ₂ EtSiH）是最合适的聚合反应控制试剂。DAAms的化学结构显着影响聚合反应的活性。例如，使用Me ₂聚合N，N-二乙基丙烯酰胺（DEtAAm）EtSiH仅显示出对分子量分布的更好控制，而使用相同的H Si具有更强的侧基的N-丙烯酰基吗啉（MorAAm）提供了对分子量及其分布的精确控制。鉴于整个聚合过程均由单体活化，通过DAAm的1,4-氢硅烷化原位形成作为真正引发剂的甲硅烷基烯酮缩醛以及GTP工艺组成，针对每种具体情况详细讨论了聚合机理。情况，例如，B（C ₆ F ₅）₃催化的DEtAAm和MorAAm的聚合以及MorAAm的利用B（C ₆ F ₅的聚合））₃和Me ₃ SiNTf ₂作为双重催化体系。最后，通过功能性甲基丙烯酰胺的1,4-氢化硅烷化反应原位制备功能性甲硅烷基乙烯酮缩醛，可以方便地实现聚（N，N-二取代丙烯酰胺）（PDAAm）的α-末端官能化，而该反应没有聚合反应性。在路易斯酸催化的GTP中，其次是Me ₃ SiNTf ₂催化的DAAms的GTP。

更新日期：2016-04-04

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