Kinetic study of the atom transfer radical polymerization of n‐docosyl acrylate

Abstract

ABSTRACT:The atom transfer radical polymerization (ATRP) of n-docosyl acrylate (DA) was studied at 80°C in N,N-dimethylformamide using the carbon tetrabromide/ FeCl 3 /2,2Ј-bipyridine (bpy) initiator system in the presence of 2,2Ј-azobisisobutyronitrile (AIBN) as the source of reducing agent. The rate of polymerization exhibits first-order kinetics with respect to the monomer. The linear relationship between the molecular weight of the resulting poly(n-docosyl acrylate) with conversion and the narrow polydispersity of the polymers indicates the living characteristics of the polymerization reaction. The significant effect of AIBN on the ATRP of DA was studied keeping [FeCl 3 ]/[bpy] constant. A probable reaction mechanism for the polymerization system is postulated to explain the observed results.

Cocrystallization behavior of poly(n‐docosyl acrylate) with n‐docosanoic acid by X‐ray and differential scanning calorimetry studies

“…23 Resonances at 2.19 and 1.58 ppm correspond to -CH and -CH 2 backbone proton, respectively. 13 These results indicate that PDA was end-functionalized with the -bromine group from the catalyst. 13 Yokota et al 25 proposed a peculiar layered structure for the conventional comb-like polymers that was made up of several parallel alkyl side chains arranged on both sides of the main chain.…”

“…13 These results indicate that PDA was end-functionalized with the -bromine group from the catalyst. 13 Yokota et al 25 proposed a peculiar layered structure for the conventional comb-like polymers that was made up of several parallel alkyl side chains arranged on both sides of the main chain. They also reported that poly(n-alkyl) acrylates and methacrylates crystallize in hexagonal packing as characterized by a single Figure 4 Plot of ⌬H alkyl versus fraction of C 22 content in all n-alkyl chains (ϭ C 22 /(C 22 ϩ side chain)).…”

“…PDA with low polydispersity was prepared by atom transfer radical polymerization (ATRP) as described. 13 The polymer was further purified by repeated precipitation in tetrahydrofuran/acetone system followed drying in vacuo overnight. The number average molecular weight (M n ) of the sample was 37,100 with a polydispersity index of 1.84. n-Docosanoic acid (C 22, BDH) and tetrahydrofuran (Qualigens) were purified by standard methods.…”

“…PDA with low polydispersity was prepared by atom transfer radical polymerization (ATRP) as described 13. The polymer was further purified by repeated precipitation in tetrahydrofuran/acetone system followed drying in vacuo overnight.…”

Iron Catalysis in Organic Synthesis

“…808,809 The living character of this process was indicated by the narrow polydispersity and by the linear relationship between molecular weight of the polymer and the conversion.…”