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Branch-Controlled ATRP Via Sulfoxide Chemistry
Macromolecules ( IF 5.1 ) Pub Date : 2021-08-25 , DOI: 10.1021/acs.macromol.1c00968 Dongwoo Kim 1 , Juhyuk Do 1 , Kyungho Kim 1 , Yeonji Kim 2 , Hana Lee 2 , Bongkuk Seo 3 , Wonjoo Lee 3 , Heung Bae Jeon 2 , Hong Y. Cho 1 , Hyun-jong Paik 1
Macromolecules ( IF 5.1 ) Pub Date : 2021-08-25 , DOI: 10.1021/acs.macromol.1c00968 Dongwoo Kim 1 , Juhyuk Do 1 , Kyungho Kim 1 , Yeonji Kim 2 , Hana Lee 2 , Bongkuk Seo 3 , Wonjoo Lee 3 , Heung Bae Jeon 2 , Hong Y. Cho 1 , Hyun-jong Paik 1
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A vinyl-containing macroinimer was prepared in situ by utilizing sulfoxide chemistry in an unprecedented manner and allowed for the one-pot synthesis of hyperbranched polymers. Sulfoxide-protected haloalkanes were prepared, and their transformation into vinyl-functionalized haloalkanes through sulfoxide elimination under various reaction conditions was investigated. The protected haloalkanes were employed as an initiator for supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) in a diluted catalytic system to prepare polymers with a high chain-end functionality at a relatively low temperature. Subsequent thermal treatment yielded the macroinimers while preserving the high chain-end functionalities. When the temperature was elevated during the linear polymerization, hyperbranched polymers were afforded in a one-pot process via the in situ generations of the macroinimers. A detailed investigation revealed that the sulfoxide-modified ATRP initiator to protect the vinyl functionality on the polymer chain was successfully utilized for the synthesis of the hyperbranched polymer. This strategy is expected to aid in the synthesis of hyperbranched polymers with a tunable distance between the branch points.
中文翻译：
通过亚砜化学进行分支控制的 ATRP
通过以前所未有的方式利用亚砜化学原位制备含乙烯基的大分子单体，并允许一锅法合成超支化聚合物。制备了亚砜保护的卤代烷烃，并研究了它们在各种反应条件下通过亚砜消除转化为乙烯基官能化的卤代烷烃。受保护的卤代烷烃在稀释的催化体系中用作补充活化剂和还原剂原子转移自由基聚合（SARA ATRP）的引发剂，以在相对较低的温度下制备具有高链端官能度的聚合物。随后的热处理产生了大分子单体，同时保留了链端的高官能度。当线性聚合过程中温度升高时，超支化聚合物是通过大分子单体的原位生成在一锅法中得到的。详细研究表明，亚砜改性的 ATRP 引发剂可以保护聚合物链上的乙烯基官能团，成功用于合成超支化聚合物。该策略有望帮助合成支点之间距离可调的超支化聚合物。
更新日期：2021-09-14
中文翻译：
通过亚砜化学进行分支控制的 ATRP
通过以前所未有的方式利用亚砜化学原位制备含乙烯基的大分子单体，并允许一锅法合成超支化聚合物。制备了亚砜保护的卤代烷烃，并研究了它们在各种反应条件下通过亚砜消除转化为乙烯基官能化的卤代烷烃。受保护的卤代烷烃在稀释的催化体系中用作补充活化剂和还原剂原子转移自由基聚合（SARA ATRP）的引发剂，以在相对较低的温度下制备具有高链端官能度的聚合物。随后的热处理产生了大分子单体，同时保留了链端的高官能度。当线性聚合过程中温度升高时，超支化聚合物是通过大分子单体的原位生成在一锅法中得到的。详细研究表明，亚砜改性的 ATRP 引发剂可以保护聚合物链上的乙烯基官能团，成功用于合成超支化聚合物。该策略有望帮助合成支点之间距离可调的超支化聚合物。
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