Photoinduced Carbene Generation from Diazirine Modified Task Specific Phosphonium Salts To Prepare Robust Hydrophobic Coatings

Abstract

3-Aryl-3-(trifluormethyl)diazirine functionalized highly fluorinated phosphonium salts (HFPS) were synthesized, characterized, and utilized as photoinduced carbene precursors for covalent attachment of the HFPS onto cotton/paper to impart hydrophobicity to these surfaces. Irradiation of cotton and paper, as proof of concept substrates, treated with the diazirine-HFPS leads to robust hydrophobic cotton and paper surfaces with antiwetting properties, whereas the corresponding control samples absorb water readily. The contact angles of water were determined to be 139° and 137° for cotton and paper, respectively. In contrast, water placed on the untreated or the control samples (those treated with the diazirine-HFPS but not irradiated) is simply absorbed into the surface. Additionaly, the chemically grafted hydrophobic coating showed high durability toward wash cycles and sonication in organic solvents. Because of the mode of activation to covalently tether the hydrophobic coating, it is amenable to photopatterning, which was demonstrated macroscopically.

Surface modification of polymers with bis(arylcarbene)s from bis(aryldiazomethane)s: preparation, dyeing and characterization

“…Acetone (50ml) was added to dissolve the residue and the solution was poured to an ice/water mixture (400ml) to crystallize and filter. The solid was collected and dried in an oven (80°C, 4h) to acquire a yellow solid (95% (18). 17 (1.52g, 6.5mmol) and iron powder (3.63g, 65.0mmol) were added to a mixed solvent of EtOH/H 2 O (25ml/5ml).…”

“…Thus, since methodology for the modification often required volatile and highly reactive carbenes, high temperature and metal catalysts, carbene insertion has been largely overlooked as a method for polymer modification 14 . Recently, Hayes [15][16][17] and Ragogna 18 reported a protocol using carbenes that are generated from diazirines for the surface modification of polymers. In contrast to their approach, we have developed a new strategy of carbene insertion derived from aryldiazomethanes [19][20][21][22][23][24][25][26] , which is attractive for polymer modification because of the short synthetic route and mild reaction conditions.…”

Surface hydrophobic modification of polymers with fluorodiazomethanes

“…He et al [13,14] used CF4 plasma modification for the conversion of a hydrophilic membrane into a hydrophobic membrane but a simple, universal and efficient chemical method for the direct hydrophobic modification of a wide range of polymers would be highly desirable. Modifications have been developed [15] using carbenes [16] or nitrenes [17], and we have developed a strategy of modification through carbene inser-tion reactions derived from aryldiazomethanes [18][19][20][21][22][23][24][25], which benefits from a short synthetic route and mild reaction conditions.…”

Eco-Friendly Cellulose–Polymer Nanocomposites: Synthesis, Properties and Applications

“…Copper acetate and pyrrole were Ghiassian et al [20] poured in a vessel and heated for 1 h at 80°C, after the appearance of blue colour, the cotton wool was immersed for an hour to become black, which indicates the deposition of CuO. The fabric was washed thoroughly, dried and reserved for the deposition of CuO by immersing and shaken well for an hour with the various thiol solution in ethanol.…”