Synthesis of gradient copolymers with complexing groups by RAFT polymerization and their solubility in supercritical CO₂

Abstract

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.

Asymmetric Copolymers: Synthesis, Properties, and Applications of Gradient and Other Partially Segregated Copolymers

“…Spontaneous gradient copolymers have been obtained via catalyst transfer polycondensation, [35] catalyzed copolymerization of olefins [36] and epoxides, [37] diverse RDRP methods (ATRP, [43][44][45][46][47][48] NMP, [49][50][51][52][53][54][55][56] OMRP, [57] RAFT, [22][23][24][58][59][60][61] ) as well as cationic ring opening polymerization. [28][29][30][31][32][33] Also, the gradient-composition backbone can be used as macroinitiators to synthesize high-molecular-weight brushes.…”

“…Asymmetric copolymers have been proposed for applications (summarized as Figure ) ranging from modifying the properties of homopolymer interfaces, compatibilization of immiscible homopolymer blends, utilization as nanocarriers of compounds of pharmaceutical interest, as complexing surfactants for the extraction of metal derivatives in scCO 2 , and as polymeric sensors for solvent polarity due to the dynamic self‐assembly behavior depending on the solution environment, to constructing thermosensitive bioconjugates and drug delivery systems …”

“…Many techniques have been used for the preparation of asymmetric copolymers, including anionic [27] and cationic [28][29][30][31][32][33] polymerizations, C1 polymerization, [34] catalyst transfer polycondensation, [35] catalyzed copolymerization of olefins [36] and epoxides, [37] ring-opening metathesis polymerization (ROMP) [38][39][40][41][42] and various RDRP techniques (e.g., atom transfer radical polymerization (ATRP), [43][44][45][46][47][48] nitroxide-mediated polymerization (NMP), [49][50][51][52][53][54][55][56] organometallic-mediated radical polymerization (OMRP), [57] and reversible addition-fragmentation chain transfer (RAFT) [22][23][24][58][59][60][61] ).…”

Raspberry-like morphology of polyvinyl chloride/zinc oxide nanoparticles induced by surface interaction and formation of nanoporous foam

“…The representative 1 H NMR spectra of the P(VC-co-AAEM) template and pure PVC for comparison are presented in Fig. 50,51 The signals of the methyl groups of ketones (-CO-CH 3 ) are overlapped in the region of 2.0-2.5 ppm. From -CH 2 groups in the polyvinyl chloride chain segments, respectively.…”

Well-defined phosphonate-functional copolymers through RAFT copolymerization of dimethyl-p-vinylbenzylphosphonate

“…Unexpectedly, only two articles report the use of a p‐ vinylbenzyl phosphonic acid dialkyl ester monomer in RAFT polymerization. Lacroix‐Desmazes and coworkers synthesized gradient copolymers from diethyl‐ p ‐vinylbenzylphosphonate and 1,1,2,2‐tetrahydro perfluorodecyl acrylate and a low molar mass statistical copolymer with styrene (St) . After transformation of the phosphonate into a phosphonic acid group, the resulting polymers could act as metal complexing surfactants for supercritical carbon dioxide processes and dispersants for cerium oxide nanoparticles before the synthesis of hybrid latexes, respectively.…”