Perfluoroalkyl-philic Character of Poly(2-hydroxyethyl vinyl ether)-block-poly[2-(2,2,2-trifluoroethoxy)ethyl vinyl ether] Micelles in Water:  Selective Solubilization of Perfluorinated Compounds

Abstract

Two types of amphiphilic block copolymer, poly(2-hydroxyethyl vinyl ether)-block-poly[2-(2,2,2-trifluoroethoxy)ethyl vinyl ether] (poly(HOVE-b-TFEOVE)) (m:n ) 78:23) and poly(2-hydroxyethyl vinyl ether)-block-poly(n-butyl vinyl ether) (poly(HOVE-b-NBVE)) (m:n ) 74:23), having the same ratios of polymerization degree in hydrophilic and hydrophobic segments with the same total chain length were synthesized, and the properties of their aqueous solutions were investigated, where m and n represent number-averaged polymerization degree of HOVE and TFEOVE or NBVE, respectively. By water surface tension measurements, the critical micelle concentrations (cmc's) of poly(HOVE-b-TFEOVE) and poly-(HOVE-b-NBVE) were both estimated at 1.0 × 10 -4 mol/L. Solubilization of various fluoro and nonfluoro compounds using these polymer aqueous solutions was examined. It was confirmed that poly(HOVEb-TFEOVE) solubilized more decafluorobiphenyl than did poly(HOVE-b-NBVE), whereas poly(HOVE-b-NBVE) solubilized more 2,6-dimethylnaphthalene than did poly(HOVE-b-TFEOVE). When a mixture of decafluorobiphenyl and 2,6-dimethylnaphthalene was added to the polymer solutions, poly(HOVE-b-TFEOVE) selectively solubilized decafluorobiphenyl, while poly(HOVE-b-NBVE) solubilized 2,6-dimethylnaphthalene predominantly, which was observed by the UV absorption spectrum of the polymer solutions.

Self-association of water-soluble fluorinated diblock copolymers in solutions

“…Matsumoto et al [27,28] have confirmed by small angle X-ray scattering that the water-soluble fluorinated diblock copolymer aggregates into spherical micelles in water. Busse et al [30] have recently reported that triblock copolymer including fluorinated block also forms micelles.…”

“…Furthermore, a fluorinated block plays a role in the construction of ordered structures as a component different from a hydrophilic or oleophilic block [12]. Copolymers with fluorinated side chains have been synthesized with the expectation of such characteristics [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30].…”

Fluorine‐Containing Block Copolymers: Synthesis and Application as a Template for Nanocellular and Porous Structures Using Supercritical Carbon Dioxide

“…1,1,2-Trichlorotrifluoroethane is often effective to avoid precipitates during polymerization and to produce polymers with controlled structures (Choi et al, 1988;Percec and Lee, 1992;Vandooren et al, 1994). Similarly, a block copolymer composed of poly(2-hydroxyethyl vinyl ether) and poly(2-(2,2,2-trifluoroethoxy)ethyl vinyl ether) can be synthesized by sequential cationic polymerization of 2-(acetoxyethyl) vinyl ether and 2-(2,2,2-trifluoroethoxy)ethyl vinyl ether, followed by hydrolysis of the acetyl protecting group as shown in Figure 23.2 (Matsumoto et al, 1999;Matsumoto et al, 2000).…”

“…Polystyryllithium end capped with 1,1-diphenylethylene can completely initiate the (Percec and Lee, 1992;Matsumoto et al, 2000). polymerization of perfluoroalkyl methacrylate to give a well-defined AB diblock copolymer (A: polystyrene, B: poly(perfluoroalkyl methacrylate)), as shown in Scheme 23.2.…”

Surface properties of miscible poly(1,1,1,3,3,3‐hexafluoroisopropyl methacrylate)/phenoxy blends

“…As such, there is a need to develop new fluorinated materials that are less expensive and possess improved properties. [5][6][7][8][9][10][11] Blending of polymers offers a convenient and economical means of obtaining new materials that combine the advantages of the blend components. 12,13 For fluorinated/nonfluorinated polymer blends, the significantly lower surface energies of fluorinated polymers over their aliphatic analogs provide a substantial thermodynamic driving force for forming fluorinated surfaces.…”