Maximizing polymer livingness in nitroxide-mediated miniemulsion polymerizations

Cunningham, Michael F.; Lin, Marcus; Buragina, Catherine; Milton, Sarah G.; Ng, David C. T.; Hsu, C. C.; Keoshkerian, Barkev

doi:10.1016/j.polymer.2004.11.038

Cited by 36 publications

(45 citation statements)

References 26 publications

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“…[19,20] As far as we are aware, there are to date no systematic studies on particle size effects in NMP in miniemulsion, although scattered information exists with regards to differences between miniemulsion and bulk for TEMPO-mediated radical polymerization of S in miniemulsion. In most cases, S/TEMPO miniemulsion polymerizations using macroinitiator (polystyrene (PS)-TEMPO), [21,22] benzoyl peroxide/ TEMPO [23,24] or potassium persulfate/TEMPO [24][25][26][27] give R p values very similar to those in bulk. [28] Cunningham and coworkers [29,30] reported a strong dependence of R p in S/PS-TEMPO miniemulsion on the amount of the surfactant sodium dodecylbenzenesulfonate (SDBS) (the particle size distributions were ''nearly identical'' with a ''mean diameter'' of 150 nm), and speculated that SDBS or SDBS impurities consume nitroxide, thus resulting in an increase in R p .…”

Section: Introductionmentioning

confidence: 99%

Particle Size Effects in TEMPO‐Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion

Nakamura

Zetterlund

Okubo

2006

Macromol. Rapid Commun.

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Summary: 2,2,6,6‐Tetramethylpiperidinyl‐1‐oxy (TEMPO)‐mediated radical polymerization of styrene in aqueous miniemulsion at 125 °C using sodium dodecylbenzenesulfonate and poly(vinyl alcohol), respectively, as colloidal stabilizers has been investigated. The particle size had a dramatic effect on the polymerization process. Decreasing particle size led to a markedly higher polymerization rate, but less control and a lower degree of livingness. For particles with diameters greater than approximately 170 nm, the polymerization behavior was essentially the same as in the corresponding bulk system. By varying the particle size within an appropriate range, it is possible to tune the polymerization such that the polymerization rate is increased while still maintaining reasonable control and livingness.magnified image

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Section: Introductionmentioning

confidence: 99%

Particle Size Effects in TEMPO‐Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion

Nakamura

Zetterlund

Okubo

2006

Macromol. Rapid Commun.

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“…Currently, a large number of commercially available coatings, paints and adhesives are synthesized in dispersed aqueous media. In addition to the obvious economical and environmental advantages, the use of a dispersed aqueous media allows the polymerization to benefit from compartmentalization effects, which permits the polymerization to reach very high conversions ( X ≈ 99%) without suffering significant irreversible termination 49. For NMP, or any other controlled radical polymerization (CRP) technique, to be adopted industrially it would be beneficial to have the polymerization proceed to high conversion while still retaining the desirable characteristics of a controlled polymerization.…”

Section: Resultsmentioning

confidence: 99%

Amphiphilic Poly(4‐acryloylmorpholine)/Poly[2‐(N‐carbazolyl)ethyl acrylate] Random and Block Copolymers Synthesized by NMP

Savelyeva

Lessard

Marić

2012

Macro Reaction Engineering

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A series of random copolymers and block copolymers containing water‐soluble 4AM and fluorescent VAK are synthesized by NMP. The homopolymerizations of 4AM and VAK and 4AM/VAK random copolymerization are performed in 50 wt% DMF using 10 mol% SG1, resulting in a linear increase in $\overline {M} _{{\rm n}} $ versus conversion, and final polymers with narrow molecular weight distributions ($\overline {M} _{{\rm w}} /\overline {M} _{{\rm n}} $ < 1.4). Reactivity ratios rVAK = 0.64 ± 0.52 and r4AM = 0.86 ± 0.66 are obtained for the 4AM/VAK random copolymerization. In addition, a poly(4AM) macroinitiator is used to initiate a surfactant‐free suspension polymerization of VAK. After 2.5 h, the resulting amphiphilic block copolymer has $\overline {M} _{{\rm n}} $ = 12.6 kg · mol−1, $\overline {M} _{{\rm w}} /\overline {M} _{{\rm n}} $ = 1.48, molar composition FVAK = 0.38 with latex particle sizes between 270 and 475 nm.

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“…For TEMPO-mediated SFRP of St in miniemulsion, the rate of polymerization was greatly enhanced upon addition of ascorbic acid 174 and sodium dodecylbenzenesulfonate (SDDS). 175 This is due to the fast consumption of excess nitroxides during polymerization.…”

Section: Crp In Miniemulsionmentioning

confidence: 99%

Recent advances in controlled/living radical polymerization in emulsion and dispersion

2008

J. Polym. Sci. A Polym. Chem.

142

126

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Effective ways to conduct controlled/living radical polymerization (CRP) in emulsion systems are necessary for commercial latex production without significant modification of current industrial facilities. Conducting CRP in emulsion media is more complicated and more challenging than its application in homogeneous bulk. These challenges come from the intrinsic kinetics of emulsion polymerization. They include mass transport, slow chain growth mechanism, and exit of short radicals from polymeric particles. This review describes the recent developments of CRP in heterogeneous dispersion, including miniemulsion, microemulsion, dispersion, and especially emulsion. Various approaches for conducting emulsion CRP are detailed, including controlled seeded emulsion polymerization, nanoprecipitation, use of short oligomers as macroinitiators for in situ block copolymerization, and RAFT-mediated selfassembly. In addition many remaining challenges of the current methods barring wide spread industrial application of emulsion CRP are also suggested.

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Maximizing polymer livingness in nitroxide-mediated miniemulsion polymerizations

Cited by 36 publications

References 26 publications

Particle Size Effects in TEMPO‐Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion

Particle Size Effects in TEMPO‐Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion

Amphiphilic Poly(4‐acryloylmorpholine)/Poly[2‐(N‐carbazolyl)ethyl acrylate] Random and Block Copolymers Synthesized by NMP

Recent advances in controlled/living radical polymerization in emulsion and dispersion

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