Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

Handle URI:
http://hdl.handle.net/10754/563169
Title:
Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis
Authors:
O'Shea, John Paul; Solov'eva, Vera A.; Guo, Xianrong; Zhao, Junpeng; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Rodionov, Valentin
Abstract:
A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Analytical Core Lab; Chemical Science Program; Core Labs; Polymer Synthesis Laboratory
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Polym. Chem.
Issue Date:
2014
DOI:
10.1039/c3py01368e
Type:
Article
ISSN:
17599954
Sponsors:
Funding from KAUST OCRF (award project "Catalysis With Soft Materials") is acknowledged with thanks.
Appears in Collections:
Articles; Analytical Core Lab; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorO'Shea, John Paulen
dc.contributor.authorSolov'eva, Vera A.en
dc.contributor.authorGuo, Xianrongen
dc.contributor.authorZhao, Junpengen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorRodionov, Valentinen
dc.date.accessioned2015-08-03T11:37:22Zen
dc.date.available2015-08-03T11:37:22Zen
dc.date.issued2014en
dc.identifier.issn17599954en
dc.identifier.doi10.1039/c3py01368een
dc.identifier.urihttp://hdl.handle.net/10754/563169en
dc.description.abstractA number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.en
dc.description.sponsorshipFunding from KAUST OCRF (award project "Catalysis With Soft Materials") is acknowledged with thanks.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleSequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysisen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentAnalytical Core Laben
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentCore Labsen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalPolym. Chem.en
kaust.authorGuo, Xianrongen
kaust.authorZhao, Junpengen
kaust.authorHadjichristidis, Nikolaosen
kaust.authorRodionov, Valentinen
kaust.authorO'Shea, John Paulen
kaust.authorSolov'eva, Vera A.en
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