PMMA‐co‐PHFBA‐co‐PHPA acrylic fluoropolymers via an ab initio emulsion atom transfer radical polymerisation with activators regenerated by electron transfer

The purpose of this paper is to synthesise the tercopolymer PMMA‐co‐PHFBA‐co‐PHPA in an ab initio emulsion through activators regenerated by electron transfer for atom transfer radical polymerisation in the absence of F‐containing surfactant and organic assistants.

To produce the tercopolymer of methyl methacrylate, hexafluorobutyl acrylate, and 2‐hydrothyl propyl acrylate with a precise macromolecular composition and structure, water used as the dispersion medium, Tween‐80 and SDS as emulsifiers, soluble ascorbic acid as the reducing agent and benzyl bromide as the initiator. The catalyst was CuBr₂/O‐phenanthroline complex. The molecular structure of the polymer was characterised by FT‐IR, Raman, and ¹H‐NMR. Molecular weight and molecular weight distributions were measured by gel permeation chromatography.

The polymer molecular composition and structure are controllable during polymerisation as defined without nitrogen protection. However, the average molecular weight of the polymer deviates from the theoretical value when the monomer fractional conversion reaches 90 percent. The molecular weight distribution of the polymer (PDI=1.4) is much broader than those done in bulk or solution polymerisation.

Integrating ab initio emulsion with activators regenerated by electron transfer via atom transfer radical polymerisation (ARGET‐ATRP) technologies could be a significant method for producing functional acrylic‐fluoropolymer with defined macromolecular composition and structure, even in the absence of F‐containing surfactant and organic assistants, both of which are necessary in the normal case.