Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators

Summary: Ultra-high-molecular-weight (UHMW) polymers can display outstanding properties; however, it is challenging to synthesize UHMW polymers by using external free radical initiators. To address this, here, we report the ration design and adoption of B-alkylcatecholborane (RBCat) as a radical ini...

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Main Authors:	Yinling Wang, Qianyi Wang, Xiangcheng Pan
Format:	Article
Language:	English
Published:	Elsevier 2020-06-01
Series:	Cell Reports Physical Science
Subjects:	B-alkylcatecholborane oxygen RAFT UHMW polymers CRP
Online Access:	http://www.sciencedirect.com/science/article/pii/S2666386420300680

id	doaj-89a8ad1b3a5a4bfc8dd0afaf630ea83c
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spelling	doaj-89a8ad1b3a5a4bfc8dd0afaf630ea83c2020-11-25T04:05:22ZengElsevierCell Reports Physical Science2666-38642020-06-0116100073Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical InitiatorsYinling Wang0Qianyi Wang1Xiangcheng Pan2State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, ChinaState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, ChinaState Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China; Corresponding authorSummary: Ultra-high-molecular-weight (UHMW) polymers can display outstanding properties; however, it is challenging to synthesize UHMW polymers by using external free radical initiators. To address this, here, we report the ration design and adoption of B-alkylcatecholborane (RBCat) as a radical initiator in controlled radical polymerization in the presence of a chain-transfer agent. The autoxidation of RBCat with one alkyl substituent generates only one alkyl radical. The oxygen is incorporated and stored in the oxidized form (ROOB-Cat) that slowly releases the alkyl radical. The rationally designed alkyl radical is proposed to preferentially activate the chain-transfer agent (CTA) and grow the polymer chain from CTA, so limited free polymer chains are formed from the initiating alkyl radicals. Polymerizations of (meth)acrylates are achieved with narrow molecular weight distribution (Ð = 1.10) and predetermined molecular weights even in a UHMW range (up to 3 million). The successful chain extension of UHMW indicates the high degree of control of the polymerization.http://www.sciencedirect.com/science/article/pii/S2666386420300680B-alkylcatecholboraneoxygenRAFTUHMW polymersCRP
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Yinling Wang Qianyi Wang Xiangcheng Pan
spellingShingle	Yinling Wang Qianyi Wang Xiangcheng Pan Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators Cell Reports Physical Science B-alkylcatecholborane oxygen RAFT UHMW polymers CRP
author_facet	Yinling Wang Qianyi Wang Xiangcheng Pan
author_sort	Yinling Wang
title	Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators
title_short	Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators
title_full	Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators
title_fullStr	Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators
title_full_unstemmed	Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators
title_sort	controlled radical polymerization toward ultra-high molecular weight by rationally designed borane radical initiators
publisher	Elsevier
series	Cell Reports Physical Science
issn	2666-3864
publishDate	2020-06-01
description	Summary: Ultra-high-molecular-weight (UHMW) polymers can display outstanding properties; however, it is challenging to synthesize UHMW polymers by using external free radical initiators. To address this, here, we report the ration design and adoption of B-alkylcatecholborane (RBCat) as a radical initiator in controlled radical polymerization in the presence of a chain-transfer agent. The autoxidation of RBCat with one alkyl substituent generates only one alkyl radical. The oxygen is incorporated and stored in the oxidized form (ROOB-Cat) that slowly releases the alkyl radical. The rationally designed alkyl radical is proposed to preferentially activate the chain-transfer agent (CTA) and grow the polymer chain from CTA, so limited free polymer chains are formed from the initiating alkyl radicals. Polymerizations of (meth)acrylates are achieved with narrow molecular weight distribution (Ð = 1.10) and predetermined molecular weights even in a UHMW range (up to 3 million). The successful chain extension of UHMW indicates the high degree of control of the polymerization.
topic	B-alkylcatecholborane oxygen RAFT UHMW polymers CRP
url	http://www.sciencedirect.com/science/article/pii/S2666386420300680
work_keys_str_mv	AT yinlingwang controlledradicalpolymerizationtowardultrahighmolecularweightbyrationallydesignedboraneradicalinitiators AT qianyiwang controlledradicalpolymerizationtowardultrahighmolecularweightbyrationallydesignedboraneradicalinitiators AT xiangchengpan controlledradicalpolymerizationtowardultrahighmolecularweightbyrationallydesignedboraneradicalinitiators
_version_	1724434400245972992

Controlled Radical Polymerization toward Ultra-High Molecular Weight by Rationally Designed Borane Radical Initiators

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