o -nitrobenzyl acrylate is polymerizable by single electron transfer-living radical polymerization

Abstract

Polymers containing o-nitrobenzyl esters are promising for preparation of light sensitive materials. o-Nitrobenzyl methacrylate has already been polymerized by controlled ATRP or RAFT. Unfortunately, the radical polymerization of o-nitrobenzyl acrylate (NBA) was not controlled until now due to inhibition and retardation effects coming from the nitro-aromatic groups. Recent developments in the Single Electron TransferLiving Radical Polymerization (SET-LRP) provide us an access to control this NBA polymerization and living character of this NBA SET-LRP is demonstrated. Effects of CuBr 2 and ligand concentrations, as well as Cu(0) wire length on SET-LRP kinetics are shown presently. A first-order kinetics with respect to the NBA concentration is observed after one induction period. SET-LRP proceeds with a linear evolution of molecular weight and a narrow distribution. High initiation efficiency close to 1 and high chain-end functionality (93%) are reached. Chain extension of poly(o-nitrobenzyl acrylate) is realized with methyl acrylate (MA) to obtain well defined poly(o-nitrobenzyl acrylate)-b-poly(methyl acrylate) (PNBA-b-PMA). Finally, lightsensitive properties of PNBA are checked upon UV irradiation.

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

“…The temperature is maintained at 0°C for the duration of the polymerization. 83 and oligo(ethylene oxide) methyl ether acrylate (OEOMEA) 38,84,85 have also been reported to be compatible with SET-LRP. Careful optimization of the solvent system (see section 3.2) allows access to the SET-LRP of long alkyl monomers, including lauryl acrylate (LA), 86 octadecyl acrylate (OA), 86 and semifluorinated acrylates 87,88 (e.g., 1H,1H,2H,2H-perfluorooctyl acrylate (PFOA), 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA), 1H,1H,5H-octafluoropentyl acrylate (OFPA), 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA)).…”

Photo‐responsive amphiphilic poly(α‐hydroxy acids) with pendent o‐nitrobenzyl ester constructed via copper‐catalyzed azide‐alkyne cycloaddition reaction

“…[11] Thereafter, different strategies for the construction of photo-responsive polymers with o-NB esters in the main chain as well as in the side chain are developed. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] However, there have been limited reports on the synthesis of biocompatible and biodegradable polymers with pendent o-NB esters group. Almutairi reported the synthesis of a polycaprolactone with pendent o-NB ester group, and demonstrated the light-controlled depolymerization of the polymers.…”

Amphiphilic photosensitive dextran-g-poly(o-nitrobenzyl acrylate) glycopolymers

“…4b). By comparison with PNBA homopolymers, one can conclude that dextran 391 part in the copolymer doesn't prevent the PNBA photolysis but delay it as the absorbance at 325 392 nm reach a plateau value after 400 s in case of PNBA homopolymers(Soliman et al, 2014).…”

“…Homopolymerization of NBA by SET-LRP: Synthesis of PNBA-Br (Scheme 1b).128 As previously reported(Soliman et al, 2014), schlenk tube was evacuated and filled by nitrogen. Me 6 TREN, 0.1 eq of CuBr 2 and of Me 6 TREN) and 7 mL DMSO were successively added 132 under N 2 flow.…”

“…PNBA 3500 -Br and PNBA 9800 -Br were prepared by SET-LRP (Scheme 1b) that was carried out under adequate experimental conditions(Soliman et al, 2014) using the respective initial molar instance, after purification, PNBA 9800 -Br were analyzed by 1 H NMR and SEC. A really good agreement was obtained between the theoretical molecular weights calculated from the 1).…”