Abstract
Vinylidene fluoride (VDF)-based copolymers bearing pendant trialkoxysilane groups for potential applications for coatings were synthesized via a free radical copolymerization of VDF with functional 2-trifluoromethyl acrylate cyclic carbonate monomer (MAF-cyCB), followed by introduction of silane pendant groups. MAF-cyCB was prepared from 2-trifluoromethacrylic acid with 70% overall yield. Radical copolymerization of VDF with MAF-cyCB initiated by tert-amyl peroxy-2-ethylhexanoate at varying [VDF]0/[MAF-cyCB]0 ratios led to several poly(VDF-co-MAF-cyCB) copolymers having different molar percentages of VDF (77−96%). The average molecular weights (Mns) reached up to 19 000 g mol−1 in fair to good yields (45−74%). Compositions and microstructures of all synthesized copolymers were achieved by 1H and 19F NMR spectroscopies. The resulting poly(VDF-co-MAF-cyCB) copolymers exhibited moderately high melting temperature (131−161 °C, with respect to the VDF content) while the degree of crystallinity, which reached up to 34%, decreased with increasing MAF-cyCB. Then, the pendant cyclic carbonate ester groups of the synthesized poly(VDF-co-MAF-cyCB) copolymers were quantitatively converted into novel triethoxysilane-functionalized PVDF, which could be further hydrolyzed under acidic conditions into trihydroxysilanefunctionalized PVDF. Finally, steel plates were coated with the silylated PVDF and displayed improved adhesion properties compared to those of pristine PVDF.