Nitroxide-mediated living radical polymerization in dispersed systems

Cunningham, Michael L.; Lin, Marcus; Smith, Jodi-Anne; Ma, John; McAuley, Kimberley B.; Keoshkerian, Barkev; Georges, Michel

doi:10.1007/978-3-540-36474-0_18

Cited by 10 publications

(14 citation statements)

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“…In Canada at this time, the TEMPO‐mediated systems were maturing, with dramatic jumps in understanding of the process, in particular by the Cunningham group at Queen's University in the area of dispersed aqueous systems. [ 7,8,74 ] They made major contributions in ab initio miniemulsion polymerizations, [ 75–78 ] such as rate enhancements, [ 79 ] partitioning of the nitroxide, [ 80,81 ] and the effect of nitroxide/initiator ratio. [ 75,82 ] Miniemulsions were easier to study as the particle nucleation step is less complicated, and technically of more interest, as it is much easier to incorporate additives like pigments, dyes, and waxes to make a composite particle (hence, XRCC adopted this direction).…”

Section: The 2000smentioning

confidence: 99%

History of nitroxide mediated polymerization in Canada

Marić

2021

Can J Chem Eng

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Nitroxide mediated polymerization (NMP), sometimes known as stable free radical polymerization (SFRP), is considered one of the main types of reversible deactivation radical polymerization (RDRP) that have emerged as a major advance in polymer synthesis in the past 30 years. This review examines NMP's development from a uniquely Canadian perspective. Inspired by reports of a reversible equilibrium between the TEMPO persistent radical and a growing polymeric radical chain, researchers at the Xerox Research Centre of Canada (XRCC) reported radical polymerizations of styrene with hallmarks typically associated with living polymerizations: linear degree of polymerization of with conversion, narrow molecular weight distributions, and ability to re‐initiate the chain end with additional monomer. This effort expanded to polymerizations in dispersed aqueous media (eg, miniemulsion) and to polymerizations directed for various architectures (block, graft, star), but NMP was ultimately generally limited to styrenic monomers. Consequently, NMP trailed other RDRP methods, such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer polymerization (RAFT), due to its limited monomer choice. With the advent of second‐generation alkoxyamine initiators, however, the range of monomers polymerizable in a controlled manner greatly expanded to include acrylates, acrylamides, and eventually methacrylates (under certain conditions), providing renewed impetus towards using NMP. Consequently, Canadian researchers applied these new alkoxyamines for more versatile polymers, resulting in products such as stimuli‐responsive polymers, CO2‐switchable latexes, bio‐hybrid composites, organic photovoltaic materials, and photolithographic materials. The chronological progression of the developments in NMP from various Canadian laboratories highlights these achievements in new polymeric materials.

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Section: The 2000smentioning

confidence: 99%

History of nitroxide mediated polymerization in Canada

Marić

2021

Can J Chem Eng

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“…[53] However, until 2007, research on RDRP techniques in dispersed states remained fairly fundamental, of which there are many reviews on this topic. [52][53][54][55][56][57][58][59][60][61] Since overcoming many of the obstacles initially presented, much of the present work points to applying these to synthesise nanomaterials geared towards a range of applications.…”

Section: Introductionmentioning

confidence: 99%

Controlled radical polymerization in dispersed systems for biological applications

Gurnani

Perrier

2020

Progress in Polymer Science

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“…CRP techniques do not require rigorous purification conditions to obtain well‐defined polymers; therefore, small amounts of impurities are tolerated . Among various techniques currently used for CRP, reversible addition‐fragmentation chain transfer polymerization (RAFT), nitroxide‐mediated polymerization (NMP), and atom transfer radical polymerization (ATRP) are the most popular ones…”

Section: Introductionmentioning

confidence: 99%

Pyrrolidone‐functional smart polymers via nitroxide‐mediated polymerization

Savelyeva

Marić

2014

J. Polym. Sci. Part A: Polym. Chem.

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Nitroxide-mediated polymerization (NMP) of N-(2methacryloyloxyethyl) pyrrolidone (MAEPYR) with 2-([tertbutyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino]oxy)-2methylpropanoic acid (BlocBuilder) initiator and N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] (SG1) nitroxide permitted controlled synthesis of poly(N-(2-methacryloyloxyethyl)pyrrolidone-stat-9-(4-vinylbenzyl)-9H-carbazole) (poly(MAEPYRstat-VBK)) statistical copolymers. With at least 5 mol % VBK, the dispersity -D of the copolymers was below 1.4 at conversions less than 50%. At conversions higher than 50%, and at lower VBK feed content, there was a significant amount of termination reactions, which broadened the molecular weight distribution of the final polymers ( -D 5 1.4-2.3). The MAEPYR-rich statistical copolymers were subsequently tested for thermoresponsive behavior in aqueous media. The cloud point tempera-tures (CPTs) in aqueous solution were tuned by changing the VBK composition, solution concentration, and heating rate, and the transitions were thermally reversible with partial loss of reversibility at higher heating rates. The CPT decreased from 59.0 to 49.7 C with addition of only 1 mol % of VBK in the copolymer, and at more than 6 mol % VBK, the copolymer was water insoluble.

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Nitroxide-mediated living radical polymerization in dispersed systems

Cited by 10 publications

References 0 publications

History of nitroxide mediated polymerization in Canada

History of nitroxide mediated polymerization in Canada

Controlled radical polymerization in dispersed systems for biological applications

Pyrrolidone‐functional smart polymers via nitroxide‐mediated polymerization

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