Hydrogen Peroxide Induced Efficient Mineralization of Poly(vinylidene fluoride) and Related Copolymers in Subcritical Water

Decompositions of poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride- co -chlorotrifluoroethylene) copolymer (poly(VDF- co -CTFE)), and poly(vinylidene fluoride- co -hexafluoropropylene) copolymer (poly(VDF- co -HFP)) in subcritical water were investigated with the aim of developing a technique to recover the fluorine component. By use of H 2 O 2, these (co)polymers can be efficiently mineralized at a relatively low temperature (300 °C). When PVDF was heated with 3.0 M H 2 O 2 for 6 h, which corresponds to 31 times the molar amount of fluorine and 32 times the molar amount of carbon in the polymer, both F – and CO 2 yields reached 98%. Poly(VDF- co -CTFE) copolymer was also mineralized under the same reaction conditions (the yields of F –, CO 2, and Cl – were 98, 95, and 97%, respectively). Poly(VDF- co -HFP) copolymer was more readily decomposed than poly(VDF- co -CTFE), leading to almost complete mineralization (F – yield, 96%; CO 2 yield, 92%) with 2.0 M H 2 O 2 . Addition of stoichiometric Ca(OH) 2 to the reactions formed CaF 2 well-identified by X-ray diffraction spectrometry.