Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†

Handle URI:
http://hdl.handle.net/10754/604376
Title:
Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†
Authors:
Alkayal, Nazeeha ( 0000-0002-3613-5789 ) ; Durmaz, Hakan; Tunca, Umit; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 )
Abstract:
Novel well–defined polyethylene–based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using the PE-OH as macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) “click” linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC).
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC); Polymer Synthesis Laboratory
Citation:
Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry† 2016 Polym. Chem.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Polym. Chem.
Issue Date:
30-Mar-2016
DOI:
10.1039/C6PY00331A
Type:
Article
ISSN:
1759-9954; 1759-9962
Sponsors:
Research reported in this publication was supported by the King Abdullah University of Science and Technology.
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2016/PY/C6PY00331A
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorAlkayal, Nazeehaen
dc.contributor.authorDurmaz, Hakanen
dc.contributor.authorTunca, Umiten
dc.contributor.authorHadjichristidis, Nikolaosen
dc.date.accessioned2016-04-04T13:16:52Zen
dc.date.available2016-04-04T13:16:52Zen
dc.date.issued2016-03-30en
dc.identifier.citationWell-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry† 2016 Polym. Chem.en
dc.identifier.issn1759-9954en
dc.identifier.issn1759-9962en
dc.identifier.doi10.1039/C6PY00331Aen
dc.identifier.urihttp://hdl.handle.net/10754/604376en
dc.description.abstractNovel well–defined polyethylene–based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using the PE-OH as macroinitiator, (ii) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (iii) “click” linking reaction to afford the PE-based graft terpolymers. All intermediates and final products were characterized by high-temperature size exclusion chromatography (HT-SEC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and differential scanning calorimetry (DSC).en
dc.description.sponsorshipResearch reported in this publication was supported by the King Abdullah University of Science and Technology.en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2016/PY/C6PY00331Aen
dc.rightsArchived with thanks to Polym. Chem.en
dc.titleWell-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†en
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalPolym. Chem.en
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul, Turkeyen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorAlkayal, Nazeehaen
kaust.authorHadjichristidis, Nikolaosen
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