Nanoreactors for Polymerizations and Organic Reactions

Abstract

The aim of this Perspective is to use the knowledge of the underpinning kinetic and thermodynamic precepts that govern free-radical and “living” radical water-based heterogeneous polymerizations and apply this to small molecule organic reactions in nanoreactors. The difficulty in applying “living” radical polymerization to water-based heterogeneous systems has led to such an understanding, including partitioning of agents between the phases, nucleation of particles, and other phenomena including superswelling. This knowledge has allowed us to prepare polymers in heterogeneous systems with well-defined molecular weight distributions and particle size distributions. However, to overcome the physical chemistry constraints, researchers had to develop complex nanoreactor systems. For the field of small molecule organic reactions in heterogeneous systems to be industrially relevant and to grow rapidly, such physical chemistry precepts should be more greatly developed.

Emulsion polymerization of styrene using irreversible addition–fragmentation chain transfer agents: effect on the course of the polymerization and molecular weight

“…Narrow PS standards were used to generate the calibration curve. 1 H NMR spectra were recorded on a Bruker AV400MHz NMR spectrometer. CDCl 3 was used as solvent.…”

“…Emulsion polymerization is a unique technique that could produce polymers under environmentally-friendly process in large-scale production [1]. Various advantages of this technique include fast polymerization rate, high monomer conversion, environmentally-friendly process using water as a reaction medium and facile heat dissipation through the aqueous phase, thus, many important polymers are manufactured by this technology, especially synthetic rubber [2,3].…”

Living Radical Polymerization by the RAFT Process – A Third Update

“…Several reviews that relate to the use of RAFT in heterogeneous media have appeared [32,96,97] including a tutorial review on RAFT in microemulsion. [32] Examples of RAFT polymerizations in heterogeneous media are included in Tables 3-14 and are distinguished in the tables by the monomer appearing in italics.…”

“…[62] The process is also given substantial coverage in most recent reviews that, in part, relate to polymer synthesis, living or controlled polymerization or novel architectures. Some of those that include significant mention of RAFT polymerization include reviews on RDRP, [63] mechanism and reagent design, [11,64,65] click chemistry, [66][67][68][69][70][71][72] synthesis of telechelics, [73] the polymerization of carbazole-containing monomers, [74] N-vinyl-1,2,3-triazoles, [75] N-vinyl heterocycles, [76] fluoro-monomers, [77] and glycomonomers, [78][79][80] synthesis of metallopolymers, [81] conjugated block copolymers, [82] dye-functionalized polymers, [83] stimuliresponsive polymers, [84,85] complex architectures, [86,87] polyolefin blocks, [88] biopolymer-polymer conjugates and bioapplications, [59,[89][90][91][92][93] polysaccharide modification, [94,95] polymerization in heterogeneous media, [96,97] microwave-assisted polymerization, [65,98,99] industrial prospects for RDRP, [100,…”

RAFT-mediated emulsion polymerization of styrene with a thermoresponsive MacroCTA

“…[1][2][3][4][5][6][7][8] Heterogeneous RAFT polymerization would seem to be the most attractive to industry compared with other 'living' radical polymerization techniques due to ease of implementation. 1,8 All that would be required is the substitution of conventional chain transfer agents with that of RAFT agents without a change in reactor design or reaction conditions.…”