Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties

Ten fluoromonomers of structure (RFO)2P(O)OCH2CH2OC(O)CRCH2 were made in 30–64% yield by treating the chloridates (RFO)2P(O)Cl with HOCH2CH2OC(O)CRCH2 in chloroform in the presence of triethylamine [RF=CF3CH2, C2F5CH2, C3F7CH2, C4F9CH2, C4F9CH2CH2 or C6F13CH2CH2; R  H or Me]. The chloromonomer (CCl3CH2O)2P(O)OCH2CH2OC(O)CHCH2 was obtained analogously in 29% yield. Polymerisation of the acrylate monomers, but not the methacrylate monomers, could be effected using α-azoisobutyronitrile as a radical initiator. Acrylic polymers having CF3CH2O, CCl3CH2O and C6F13CH2CH2O side-chains were obtained as translucent rubbers. Specimens of cotton fabric were treated with solutions of the polymers, and average water and oil repellency ratings measured. Fabric coated with the polymer with the C6F13CH2CH2O side-chain afforded protection from penetration of the test liquids. Treated fabrics were subjected to the limiting oxygen index (LOI) test according to BS EN ISO 4589-2 (1999): this test determines the point at which a material just burns in a volumetric flow of oxygen and nitrogen. The treated fabrics were more fire-resistant (LOI 22–29%) than the untreated fabric (LOI 18%). Fabric coated with the CCl3CH2O-based polymer can be considered fire-retardant (LOI 29%). The fluoromonomers were tested for anti-acetylcholinesterase activity and were found to be poor enzyme inhibitors; they are predicted to possess low acute toxicity.