NDLI: First RAFT/MADIX radical copolymerization of tert-butyl 2-trifluoromethacrylate with vinylidene fluoride controlled by xanthate

Content Provider	Royal Society of Chemistry (RSC)
Author	Ameduri, Bruno Patil, Yogesh
Copyright Year	2013
Abstract	The radical copolymerization of tert-butyl 2-trifluoromethacrylate (MAF-TBE) with vinylidene fluoride (VDF), initiated by bis(4-tert-butyl cyclohexyl) peroxydicarbonate and controlled by O-ethyl-S-(1-methyloxycarbonyl) ethyl xanthate as a chain transfer agent (CTA) is presented. Molar masses ranged between 1500 and 50 000 g mol−1 while polydispersity indices (PDIs) were lower than 1.8. Various experimental conditions such as different radical initiators, solvents, initial [initiator]o/([VDF]o + [MAF-TBE]o) and [CTA]o/([VDF]o + [MAF-TBE]o) molar ratios, and their effect on the copolymerization (in terms of molar percentages of both comonomers in the copolymer, yields, molar masses, and thermal properties) were examined and discussed. These poly(VDF-co-MAF-TBE) copolymers bearing a xanthate end-group were further involved in controlled radical polymerizations of vinyl acetate (VAc) or VDF leading to poly(VDF-co-MAF-TBE)-b-poly(VAc) and poly(VDF-co-MAF-TBE)-b-poly(VDF) block copolymers, respectively. The success of these radical copolymerizations of MAF-TBE contrasts with its homopolymerization that occurred with difficulty and produced low molecular weight-homopolymers in low yields. On the other hand, the controlled character of the polymerization involving O-ethyl-S-(1-methyloxycarbonyl) ethyl xanthate was confirmed by the evolutions of log([M]o/[M]) and MAF-TBE conversion versus time and by size exclusion chromatography that were found to be linear. All the structures of the obtained intermediates and block copolymers were characterized by 1H and 19F NMR spectroscopy and size exclusion chromatography to assess the molar percentages of VDF and MAF-TBE and the molecular weights and PDIs, respectively. The thermal and surface properties of such original copolymers were determined by thermogravimetric analysis and water contact angle measurements, respectively.
Starting Page	2783
Ending Page	2799
Page Count	17
File Format	HTM / HTML PDF
ISSN	17599954
Volume Number	4
Issue Number	9
Journal	Polymer Chemistry
DOI	10.1039/c3py21139h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Dispersity End-group Thermogravimetric analysis Molar mass Butyl group Polymerization 1,1-Difluoroethylene Fluorine-19 nuclear magnetic resonance List of Chicago Transit Authority bus routes Water contact CTA Chain transfer Xanthate VDF Size-exclusion chromatography Copolymer Nuclear magnetic resonance Vinyl acetate
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Bioengineering Biomedical Engineering Polymers and Plastics

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