Blocklike Fluorocarbon and Hydrocarbon Copolymer Films via Surface-Initiated ATRP and Postpolymerization Reactions

Abstract

We report a new method to prepare ultrathin blocklike copolymer films on metal surfaces with molecularly optimized surface and barrier properties. Copolymer films containing various fluorocarbon and/or hydrocarbon side chains were created by a one-step surface-initiated polymerization of poly-(hydroxyethyl methacrylate) (PHEMA) followed by straightforward derivatization steps. Exposure of PHEMA to perfluorobenzoyl chloride results in a perfluoroaryl-modified PHEMA film that exhibits high conversion and outstanding barrier properties but does not present an oleophobic surface. We have previously demonstrated that fluorinated esters created in this manner may be hydrolyzed back to PHEMA by brief exposure to base. Controlled hydrolysis results in regeneration of PHEMA in the outer surface region that can be subsequently rederivatized with alkyl or fluoroalkyl acid chlorides to create copolymer films with tailored surface composition. Surface properties are solely affected by the species used during rederivatization while barrier properties result from the combined conversion, structuring, and surface properties of the copolymer film.

Studies of fluorinated methylacrylate copolymer on the surface of cotton fabrics

“…As shown in Table 3, F-content decreases with an increase of take-off angle (or analysis depth), indicating a higher concentration of fluorine at air-polymer interface than bulk level. The trend of fluorine enrichment at the air-polymer interface is coincident with previous research results about fluorine-containing (methyl)acrylate copolymer film, [42][43][44][45][46] but there is an obvious difference between film surface and fabric surface, that F-content reduced more slowly with increasing takeoff angle on the fabric surface than on pure polymer film. Surface of pure polymer film is smoother than the fabric surface which has a lot of thin fuzz, so that the effective analysis depth is shallower for the fabric surface at the same take-off angle.…”

“…40,41 The surface analysis and surface properties of copolymers has been studied using the copolymer latex thin films which have been cast or coated on polyethylene terephthalate, glass plate, silicon substrates, aluminum substrates, HDPE, PVC, PTFE, etc. [42][43][44][45][46] In our recent work, we have succeeded in preparing a methylacrylate copolymer latex using 2-(perfluoroctyl) ethyl methylacrylate (PFOMA), stearyl methylacrylate (SMA), n-hydroxylethyl methylacrylate (HEMA) and n-butyl acrylate (BA) as monomers, by traditional emulsion polymerization, and have treated some pure cotton woven fabrics using it as a water and oil repellent at different curing temperatures and times. The treated fabric samples were investigated by angledependent XPS (ADXPS) and attenuated total reflectance infrared analysis (ATR IR) directly.…”

Efficient Two-Step Synthesis of 11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a Conventional Initiator for Grafting Polymer Brushes from Gold Surfaces via ATRP

“…In the second step, we observed a messy reaction when using the strong acylating agent 2-bromoisobutyryl bromide and triethylamine as base according to the seminal procedure by Shah et al [5] (synthesis I), which was cited and utilized for the synthesis of diester 3 in numerous subsequent publications [3,4,[11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] without substantial modification.…”

Formation of surface-grafted polymeric amphiphilic coatings comprising ethylene glycol and fluorinated groups and their response to protein adsorption

“…[21][22][23][24][25] Three different acylchlorides were employed ͑all obtained from Sigma-Aldrich͒: heptafluorobutyryl chloride ͑C 3 F 7 COCl, F3͒, pentadecafluoro-octanoyl chloride ͑C 7 F 15 COCl, F7͒, and pentafluorobenzoyl chloride ͑C 6 F 5 COCl, PFA͒. Substrates with PHEMA brushes were exposed to 80 mM solutions of a given acylchloride with 100 mM pyridine in dichloromethane for 24 h at room temperature to modify PHEMA films with fluorinated side chains ͑see Fig.…”