Synthesis and Performance of Novel Fluorinated Acrylate Polymers: Preparation and Reactivity of Short Perfluoroalkyl Group Containing Monomers

Abstract

Developing novel fluorinated monomers and polymer materials with a short perfluoroalkyl group is attracting the attention of researchers. The synthesis of fluorinated monomers, [N-methyl-perfluorobutane-1-sulfonamide]ethyl acrylate (C 4 SA) and methacrylate (C 4 SMA), [N-methyl-perfluorohexane-1-sulfonamide]ethyl acrylate (C 6 SA), and methacrylate (C 6 SMA) were presented from a three-step procedure, which combined the reaction of perfluorobutanesulfonyl fluoride or perfluorohexanesulfonyl fluoride with an excess of methylamine, alkylation reaction with 2-bromoethanol, and esterification reaction with acryloyl chloride or methacryloyl chloride. The outcome compounds structures of each step were confirmed by 1 H NMR, 19 F NMR, FT-IR, and elemental analysis. Free radical copolymerizations of fluorinated acrylates and butyl methacrylate (BMA) in butyl acetate (BuOAc) were performed to determine the comonomers reactivity ratios and Q-e values. The surface wetting properties of fluorinated homopolymers were investigated by surface tension and dynamic contact angles. As a result, the target polymers showed extreme low surface energies and dynamic surface properties.

A novel block copolymer with excellent amphiphobicity synthesized via ARGET ATRP

“…We introduced an N-methylsulfonamide (NMSA) spacer group between hydrocarbon of main chain and R f side chain to induce the PFSA-C 6 organized in a liquid crystalline lamellar structure, whereas the PFA-C x s (x 6) without NMSA spacer group were found to be amorphous with poor water and oil repellencies. 2,10,16,17 The homopolymer and random copolymer of C 6 SMA synthesized via traditional radical polymerization has been reported by our group. 1,2,18 In our previous reports, attributed to the steric term and polarity of the N-methysulfonamide group that tend to facilitate the orientation of the perfluorinated segments in smectic phases, PC 6 SMA exhibited liquid crystalline lamellar structures in the bulk.…”

“…2,10,16,17 The homopolymer and random copolymer of C 6 SMA synthesized via traditional radical polymerization has been reported by our group. 1,2,18 In our previous reports, attributed to the steric term and polarity of the N-methysulfonamide group that tend to facilitate the orientation of the perfluorinated segments in smectic phases, PC 6 SMA exhibited liquid crystalline lamellar structures in the bulk. However, the amount of C 6 SMA used in the copolymer was large, 18 usually higher than 50 wt %, in order to obtain relatively well hydrophobicity.…”

“…[1][2][3][4][5] Fluoropolymers have the most excellent comprehensive properties for thermal stability, chemical resistance, 6,7 weather fastness, and so on. The -CF 2 or -CF 3 groups endow the (co)poly(perfluoroalkyl acrylate)s[PFA-C x s, where x is the CF 2(3) number of the R f groups], with exceedingly low surface energy (c c ).…”

“…However, the amount of C 6 SMA used in the copolymer was large, 18 usually higher than 50 wt %, in order to obtain relatively well hydrophobicity. 2,18 Given the cost of fluorocontaining monomer, we need to decrease C 6 SMA dosage…”

Synthesis and properties of gradient copolymers of butyl methacrylate and fluorinated acrylate via RAFT miniemulsion copolymerizations

“…Fluorinated acrylate with more than eight fluorinated carbon atoms (C8) is a perfect component to prepare functional polymer materials with super low surface energy because of the low surface molecular mobility . Unfortunately, the long perfluoroalkyl chains have been confirmed to resist degradation and bioaccumulate in human and animal tissue . More research presently has focused on developing environmentally friendly and nontoxic alternative fluorinated materials to replace the traditional perfluoroalkyl polymers.…”