In Situ Reversible Addition–Fragmentation Chain Transfer Polymerization of Styrene in the Presence of MCM‐41 Nanoparticles: Comparing “Grafting from” and “Grafting through” Approaches

Abstract

ABSTRACT:The preparation of polystyrene/MCM-41 nanocomposites was carried out by "grafting from" and "grafting through" approaches and in the presence of unmodified MCM-41, using reversible addition-fragmentation chain transfer (RAFT) polymerization. The MCM-41 was modified by attaching S-dodecyl-S -(α,α -dimethyl-α -acetic acid)trithiocarbonate (DDMAT) as the RAFT agent and methacrylate group using 3-methacryloxypropyldimethylchlorosilane. The kinetics of styrene RAFT polymerization by different approaches was compared with the model polymerization mediated by free DDMAT. The quantity of the grafted chain grown from the surface and inside of the pores of MCM-41 and free polymer chains in bulk was determined by thermogravimetric analysis. The molecular weight of the produced polymer chains increased linearly with the monomer conversion for three methods. The gel permeation chromatography showed that the molecular weight of grafted and free polymer chains in the "grafting from" approach is higher than other methods, and molecular weight distributions were relatively narrower whereas the rate of polymerization for "grafting from" was higher. C

SR&NI atom transfer radical random copolymerization of styrene and butyl acrylate in the presence of MPS-functionalized silica aerogel nanoparticles

“…In grafting through method, modification process is performed by introducing a suitable organic modifier (containing a vinyl moiety) on the surface of the nanoparticles and then these vinyl moieties can participate in the polymerization reaction [36,37]. Therefore, the hydrophilic silica aerogel nanoparticles are functionalized with double bond containing modifier (MPS) that this process is illustrated in Fig.…”

“…Surface modification via grafting method is classified into three main groups: grafting from, grafting to, and grafting through [36]. In grafting through technique, the surface modifier contains a double bond moiety that this double bond can participate in the polymerization reaction as a vinyl monomer [37].…”

Styrene and Methyl Methacrylate Random Copolymerization via AGET ATRP: Incorporation of Hydrophobic Silica Aerogel Nanoparticles

“…Therefore, copolymerization rate and conversion value decrease by the addition of nanoporous silica aerogel content. 50 (iii) An irreversible reaction between growing radicals and functional moieties on the surface of nanoporous silica aerogel changes the kinetic data and can reduce the efficiency of copolymerization. 51,52 Table II summarizes data obtained from SEC traces.…”

Synthesis of poly(2-hydroxyethyl methacrylate)-grafted poly(aminoamide) dendrimers as polymeric nanostructures

“…However, P(HEMA), as a blood compatible polymer [18], may reduce cytotoxicity of conjugated dendrimer. Among different strategies for grafting polymers onto surfaces, the Bgrafting fromm ethod [19] is the most applicable mechanism that can be combined with living and controlled polymerization mechanisms such as atom transfer radical polymerization (ATRP) [20] and reversible addition-fragmentation chain transfer (RAFT) polymerization [21] to synthesize thermoresponsive polymers.…”