Emulsion copolymerization of vinylidene fluoride (VDF) with perfluoromethyl vinyl ether (PMVE)

• Published in: Polymer chemistry 2020-03, Vol.11 (13), p.243-244
• Main Authors: Reis da Cunha, Fernando, Davidovich, Irina, Talmon, Yeshayahu, Ameduri, Bruno
• Format: Article
• Language: English
• Subjects: Autoclaving; Chemical Sciences; Copolymerization; Copolymers; Design of experiments; Fluorides; Monomers; NMR spectroscopy; Parameter identification; Polymer chemistry; Polymers; Potassium persulfate; Propionic acid; Surfactants; Thermal stability; Vinyl ethers; Vinylidene; Vinylidene fluoride
• ISSN: 1759-9954; 1759-9962
• DOI: 10.1039/d0py00059k

The radical emulsion copolymerization of vinylidene fluoride (VDF) with perfluoromethyl vinyl ether (PMVE), initiated by potassium persulfate in the presence or absence of a surfactant is presented. The surfactant used in this copolymerization was 3-hydroxy-2-trifluoromethyl propanoic acid (MAF-OH). The VDF mol% ranged between 60 and 90 mol%. Molar masses up to 103 000 g mol −1 with wide dispersities ( > 2) were produced with yields up to 74%. The composition of the resulting poly(VDF- co -PMVE) copolymers was determined by 19 F NMR spectroscopy. Under certain conditions (60% VDF mol% in the autoclave inlet, MAF-OH and a low total monomer concentration), the produced latexes were stable and showed an average particle size of ca. 200 nm, as observed using a Zetasizer and a cryo-TEM. Semi-crystalline copolymers were obtained when the VDF mol% was higher than 80 mol%. These copolymers exhibit high thermostability (their degradation under air started at 400 °C). A central point 2 3 factorial experimental design was conducted aiming at the identification of the influence of the parameters on the reaction and the end-use properties of the polymers. Most of the studied properties were highly influenced by the VDF mol%. The highest molar mass was obtained using 90 mol% VDF in the feed, no surfactant, and a total monomer molar amount of 208 mmol, while the highest dispersity was obtained using 60 mol% VDF in the feed, no surfactant, and a total monomer molar amount of 208 mmol. The radical emulsion copolymerization of vinylidene fluoride (VDF) with perfluoromethyl vinyl ether (PMVE), initiated by potassium persulfate in the presence or absence of a surfactant is presented.