Polymers derived from fluoroketones. III. Monomer synthesis, polymerization, and wetting properties of poly(allyl ether) and poly(vinyl ether)

Abstract

AbstractThe synthesis and polymerization of a series of perhaloalkyl allyl and vinyl ethers derived from perhaloketones is described. Data on the critical surface tension of wetting (γc) for high molecular weight polymers of heptafluoroisopropyl vinyl ether and low molecular weight poly(heptafluoroisopropyl allyl ether) is also presented. Preparation of the allyl ethers is a one‐step, high‐yield displacement reaction between the potassium fluoride–perhaloacetone adduct and an allyl halide, such as allyl bromide. The vinyl ethersare prepared by a two‐step process which involves displacement of halide from a 1,2‐dihaloethane with a KF–perhaloacetone adduct and dehydrohalogenation of the 1‐halo‐2‐perhaloalkoxyethane to a vinyl ether. Low molecular weight polymers were obtained with heptafluoroisopropyl allyl ether by using a high concentration of a free‐radical initiator. The low molecular weight poly(heptafluoroisopropyl allyl ether) had a γc of 21 dyne/cm. No polymer was obtained with tributylborane–oxygen or with VCl3–AIR3, with gamma radiation, or by exposure to ultraviolet light. High molecular weight polymers were obtained from heptafluoroisopropyl vinyl either by using either lauryl peroxide or ultraviolet light but not by exposure to BF3–etherate. The γc for poly(heptafluoroisopropyl vinyl ether) ranged from 14.2 to 14.6 dyne/cm., and the significance of this value is discussed in relation to the γc for poly(heptafluoroisopropyl acrylate).