Ultrafast preparation of branched poly(methyl Acrylate) through single electron transfer living radical polymerization at room temperature

Abstract

Ultrafast preparation of branched poly(methyl acrylate) (BPMA) with high‐molecular weight through single electron transfer living radical polymerization (SET‐LRP) of inimer at 25°C has been attempted, atom transfer radical polymerization (ATRP) at 60°C was also carried out for comparison. Gas chromatography, proton nuclear magnetic resonance, and triple detection size exclusion chromatography were used to analyze these polymerizations. As expected, SET‐LRP system showed much faster polymerization rate than ATRP system, the calculated apparent propagation rate constants (kpapp) are 3.69 × 10−2 min−1 and 6.23 × 10−3 min−1 for SET‐LRP and ATRP system, respectively. BPMA with high‐molecular weight (Mw.MALLS = 86,400 g mol−1) compared with that in ATRP (Mw.MALLS = 61,400 g mol−1) has been prepared. POLYM. ENG. SCI., 54:1579–1584, 2014. © 2013 Society of Plastics Engineers

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

“…Branched and dendritic macrostructures are of great interest in both academic and industrial fields due to their potential application as viscosity modifiers, catalyst supports, drug carriers, and additives. , Kong and co-workers exploited SET-LRP for the ultrafast preparation of branched PMA utilizing 2-(2-bromoisobutyryloxy) ethyl acrylate (BIBEA) as the inimer at ambient temperature . In addition, Percec and co-workers have demonstrated the synthesis of dendritic macromolecules through divergent iterative thio-bromo “click” chemistry and SET-LRP to synthesize a new class of poly­(thioglycerol-2-propionate) (PTP) dendrimers.…”

“…315,316 Kong and co-workers exploited SET-LRP for the ultrafast preparation of branched PMA utilizing 2-(2-bromoisobutyryloxy) ethyl acrylate (BIBEA) as the inimer at ambient temperature. 317 In addition, Percec and co-workers have demonstrated the synthesis of dendritic macromolecules through divergent iterative thio-bromo "click" chemistry and SET-LRP to synthesize a new class of poly(thioglycerol-2-propionate) (PTP) dendrimers. The combination of a previously reported two step iterative approach to PTP dendrimers (Figure 19) 318 with the SET-LRP of MA generated a new three-step "branch" and "grow" approach to dendritic macromolecules where PMA connects the branching subunits.…”

Light and Temperature as Dual Stimuli Lead to Self-Assembly of Hyperbranched Azobenzene-Terminated Poly(N-isopropylacrylamide)

“…Hyperbranched polymers were previously prepared through controlled/“living” radical polymerization in the presence of branching agents [ 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 ] and hence it was hypothesized that the hyperbranched poly( N -isopropylacrylamide) (PNIPAM) could also be synthesized by atom transfer radical polymerization (ATRP) of PNIPAM and N , N ′-methylenebis(acrylamide) (MBA) [ 46 , 47 , 48 ]. Therefore, the ATRP of NIPAM using different azobenzene-functional initiators was carried out using Scheme 1 under the condition of isopropyl alcohol:water = 2:1 (m/m), T = 25 °C, and [NIPAM] 0 :[MBA] 0 :[initiator] 0 :[CuCl] 0 :[Me 6 TREN] 0 = 30:0.9:1:1:3.…”

Preparation and Properties of Branched Polystyrene through Radical Suspension Polymerization

“…Moreover, star polymers were prepared in one-pot by atom transfer radical polymerization (ATRP) of maleimide inimer and styrene [ 6 ]. The SCVP of inimer strategy was also used to prepare branched vinyl polymers through living radical polymerization [ 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. To eliminate the tedious preparation process of the inimer, Baskaran and Sherrington’s group prepared branched polymers using commercially available divinyl monomer as the branching agent through anionic polymerization and ATRP, respectively [ 14 , 15 ].…”