Copolymerization of fluorinated acrylic monomers with p-vinylphenol and hydroxyethyl methacrylate

Copolymers of p-vinylphenol were prepared in bulk with heptafluorobutyl and pentadecafluorooctyl acrylates and trifluoroethyl, hexafluoroisopropyl, heptafluorobutyl, octafluoropentyl and pentadecafluorooctyl methacrylates using azobisisobutyronitrile as the initiator in sealed tubes. Intrinsic viscosities of the copolymers ranged from 0.44 to 1.85. Monomer reactivity ratios for copolymers of trifluoroethyl methacrylate (M₁) were: with hydroxyethyl methacrylate (M₂), r₁ = 0.47, r₂ = 1.0; with methyl methacrylate (M₂), r₁ = 0.82, r₂ = 0.50; with styrene (M₂), r₁ = 0.29, r₂, = 0.20; and with p-vinylphenol (M₂), r₁ = 0.096, r₂ = 1.5. Q and e values of trifluoroethyl methacrylate were 1.30 and 0.92, respectively. Monomer reactivity ratios of octafluoropentyl methacrylate (M₁) were: with styrene (M₂), r₁ = 0.26, r₂ = 0.20; and with p-vinylphenol, r₁ = 0.21, r₂ = 1.5. Q and e values for octafluoropentyl methacrylate were 1.27 and 0.92, respectively. Critical surface tensions of the homopolymers ranged from 17.9 to 14.8 dyn/cm. A copolymer of hexafluoro-i-propyl methacrylate and p-vinylphenol exhibited a critical surface tension of 16.5 dyn/cm.