Mn2(CO)10-photomediated synthesis of poly(vinylidene fluoride)-b-poly(styrene sulfonate)

0444813 - ÚMCH 2016 RIV GB eng J - Journal Article
Černoch, Peter - Petrova, Svetlana - Černochová, Zulfiya - Kim, J. S. - Simpson, C. P. - Asandei, A. D.
Mn2(CO)10-photomediated synthesis of poly(vinylidene fluoride)-b-poly(styrene sulfonate).
European Polymer Journal. Roč. 68, July (2015), s. 460-470. ISSN 0014-3057. E-ISSN 1873-1945
R&D Projects: GA MŠMT(CZ) LH14038
Institutional support: RVO:61389013
Keywords : polystyrenesulfonate * poly(neopentyl styrenesulfonate) * PVDF
Subject RIV: CD - Macromolecular Chemistry
Impact factor: 3.485, year: 2015

Mn2(CO)10-photomediated activation of perfluoro alkyl iodides under visible light was applied in the initiation of the polymerization of neopentyl styrene sulfonate (NeoSS) and of vinylidene fluoride (VDF). In the latter case, an iodine degenerative controlled radical polymerization also enabled the synthesis of PVDF-I with high chain end functionality, suitable for block copolymer synthesis. As such, quantitative Mn2(CO)10 activation of both PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends enabled the clean synthesis of PVDF-b-PNeoSS block copolymers. While subsequent deprotection of the neopentyl group was attempted by several methods, pure thermal decomposition was revealed to be more of a surface process, and while both (CH3)3Si-I and LiBr deprotections failed, NaN3 in dimethyl sulfoxide was proven to allow for a complete removal of the protecting group to cleanly afford PVDF-b-PSSNa. These procedures provide simpler, cleaner and powerful avenues towards the synthesis of well-defined sulfonated and fluorinated block copolymers for fuel cell membranes.
Permanent Link: http://hdl.handle.net/11104/0247306