We report the synthesis of new gradient fluorinated copolymers with complexing groups and soluble in supercritical carbon dioxide (scCO 2 ). Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate-co-acetoacetoxyethyl methacrylate) (poly(FDA-co-AAEM)) and poly(1,1,2,2-tetrahydroperfluorodecyl acrylate-co-vinylbenzylphosphonic acid diethylester) (poly(FDA-co-VBPDE)) gradient copolymers were synthesized by reversible addition fragmentation chain transfer polymerization in a,a,a-trifluorotoluene. Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate-co-vinylbenzylphosphonic diacid) (poly-(FDA-co-VBPDA)) gradient copolymer was efficiently obtained by cleavage of the phosphonic ester groups of poly(FDA-co-VBPDE). The cloud points of these gradient copolymers in dense CO 2 were measured in a variable volume view cell at temperatures between 25 and 65 C. The gradient copolymers show very good solubility in compressed CO 2 with the decreasing order: poly(FDA-co-AAEM) % poly(FDA-co-VBPDE) [ poly(FDA-co-VBPDA). Following a green chemistry strategy, poly(FDA-co-AAEM) gradient copolymer was successfully synthesized in scCO 2 with a good control over number-average molecular weight and composition. molar fraction of VBPDAÂMðVBPDAÞ molar fraction of VBPDAÂMðVBPDAÞþmolar fraction of FDAÂMðFDAÞ , where M(FDA) and M(VBPDA) are the molecular weights of FDA and VBPDA.
5456RIBAUT ET AL.
This work aims at demonstrating the interest of gradient copolymers in supercritical CO(2) in comparison with block copolymers. Gradient copolymers exhibit a better solubility in supercritical CO(2) than block copolymers, as attested by cloud point data. The self-assembly of gradient and block copolymers in dense CO(2) has been characterized by Small-Angle Neutron Scattering (SANS), and it is shown that it is not fundamentally modified when changing from block copolymers to gradient copolymers. Therefore, gradient copolymers are advantageous thanks to their easier synthesis and their solubility at lower pressure while maintaining a good ability for self-organization in dense CO(2).
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