RAFT for the control of monomer sequence distribution - Single unit monomer insertion (SUMI) into dithiobenzoate RAFT agents

Graeme Moad, Carlos Guerrero-Sanchez, Joris J. Haven, Daniel J Keddie, Almar Postma, Ezio Rizzardo, San H. Thang

Research output: Chapter in Book/Report/Conference proceedingConference PaperResearchpeer-review

20 Citations (Scopus)

Abstract

In this paper we explore RAFT (reversible addition-fragmentation chain transfer) single unit monomer insertion (SUMI) into dithiobenzoates. Styrene and N-isopropylacrylamide (NIPAm) were successfully inserted into 2-cyanopropan-2-yl dithiobenzoate. Attempted SUMI of methyl methacylate (MMA) provided an oligomeric insertion product due to the low transfer constant of the dithiobenzoate in MMA polymerization. A very low yield with maleic anhydride (MAH) reflects the low reactivity of MAH towards 2-cyanopropan-2-yl radicals. We also examined insertion of MAH, styrene and NIPAm into the styrene SUMI product. Insertion of MAH was rapid and efficient. SUMI with styrene and NIPAm was slower, which is attributed both to the low monomer concentrations used and the poor leaving group ability of the propagating species. The reaction with NIPAm is additionally complicated by initiator-derived by-products.

Original languageEnglish
Title of host publicationSequence-Controlled Polymers
Subtitle of host publicationSynthesis, Self-Assembly, and Properties
EditorsJean-François Lutz, Tara Y. Meyer, Makoto Ouchi, Mitsuo Sawamoto
Place of PublicationWashington DC
PublisherAmerican Chemical Society
Chapter9
Pages133-147
Number of pages15
Volume1170
ISBN (Electronic)9780841230019
DOIs
Publication statusPublished - 2014
Externally publishedYes
EventInternational Symposium on Sequence-controlled Polymers: Synthesis, Self-Assembly, and Properties / American-Chemical-Society National Meeting 2013 - Indianapolis, United States of America
Duration: 8 Sep 201312 Sep 2013
Conference number: 1st

Publication series

NameACS Symposium Series
Volume1170
ISSN (Print)00976156
ISSN (Electronic)19475918

Conference

ConferenceInternational Symposium on Sequence-controlled Polymers: Synthesis, Self-Assembly, and Properties / American-Chemical-Society National Meeting 2013
CountryUnited States of America
CityIndianapolis
Period8/09/1312/09/13
OtherThe first international symposium on sequence-controlled
polymers was organized at the 246th American Chemical Society national
meeting in Indianapolis. All the chapters in this volume are related to the
invited oral presentations that were given during the symposium

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