TEMPO‐Mediated Emulsion Polymerization

Maehata, Hideo; Liu, Xinzhi; Cunningham, Michael F.; Keoshkerian, Barkev

doi:10.1002/marc.200700750

Cited by 31 publications

(26 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Thus, an emulsion type polymerization can still proceed via homogeneous or micellar nucleation, but a miniemulsion type polymerization based on droplet nucleation would be extremely slow or completely inhibited due to the presence of inhibitor in the monomer droplets. 32,70 The conversion for polymerization in the presence of CO 2 with inhibitor at P T aer 6 h was 24%, to be compared with $100% conversion without inhibitor. These results are consistent with predominant monomer droplet nucleation.…”

Section: Figmentioning

confidence: 99%

Radical polymerization of miniemulsions induced by compressed gases

et al. 2016

View full text Add to dashboard Cite

Generation of miniemulsions (nanoemulsions) comprising hydrophobic vinyl monomers and water by use of the compressed gases carbon dioxide and ethylene, respectively, has been investigated in the absence of high energy mixing. It is proposed that transparent/translucent miniemulsions are formed at the transparency pressure (P T ) as a result of the refractive index of the dispersed phase being reduced due to expansion with carbon dioxide/ethylene, resulting in refractive index matched miniemulsions with enhanced stability. Radical polymerization of methyl acrylate at 40 C in miniemulsions induced by carbon dioxide at P T proceeds as a hybrid miniemulsion/emulsion polymerization system generating particles with diameters less than 100 nm. The experimental data are consistent with particle formation occurring mainly via monomer droplet nucleation (miniemulsion polymerization) but also via secondary nucleation in the aqueous phase (emulsion polymerization). Polymerizations at a range of pressures above and below P T revealed limited pressure effects on the polymerization rate and particle size for both carbon dioxide and ethylene.

show abstract

Section: Figmentioning

confidence: 99%

Radical polymerization of miniemulsions induced by compressed gases

et al. 2016

View full text Add to dashboard Cite

show abstract

“…[18][19][20] As a solution of the problem, Hawkett and coworkers recently proposed an emulsifier-free reversible addition-fragmentation chain transfer emulsion polymerization method utilizing self-assembly. 21,22 Following this proposal, nitroxide-mediated radical polymerization [23][24][25][26][27][28] and reversible addition-fragmentation chain transfer [29][30][31][32][33][34][35] in emulsion polymerization systems have been successfully studied.…”

Section: Introductionmentioning

confidence: 99%

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

Moribe

Kitayama

Suzuki

et al. 2011

Polym J

View full text Add to dashboard Cite

Particle formation during the initial stages of emulsifier-free organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene at 601C was investigated at two stirring rates (220 and 1000 r.p.m.), in which the styrene phase floated as a layer on an aqueous phase at 220 r.p.m. or became dispersed as droplets at 1000 r.p.m. A water-soluble TERP agent, poly(methacrylic acid) (PMAA)-methyltellanyl (PMAA 30 -TeMe) and a water-soluble thermal initiator, 4,4¢-azobis(4-cyanovaleric acid), at alkaline pH were used. The control/livingness was better at 1000 r.p.m. than at 220 r.p.m., and the particle size distribution was also affected by the stirring rate: both nanometer-sized and submicrometer-sized particles were observed at 220 r.p.m., and mainly nanometer-sized particles were observed at 1000 r.p.m. Because the percentage of PMAA 30 -TeMe consumed in the initial stage was much higher at 1000 r.p.m. than at 220 r.p.m., self-assembly nucleation preferentially occurred at 1000 r.p.m., resulting in nanometer-sized particles and good control/livingness. Stirring at 1000 r.p.m. only in the initial stage of the emulsion TERP followed by 220 r.p.m. induced good control/livingness and the formation of mainly nanometer-sized particles. It is concluded that a high stirring rate in the initial stage is important for the emulsion TERP of styrene to obtain good control/ livingness and to control the particle formation mechanism.

show abstract

“…The polymerization resulted in the formation of stable submicron-sized particles of wellcontrolled PSt with M w /M n \ 1.2 at around 50% monomer conversion, indicating that the colloidal instability with a large amount of coagulum in emulsion CRP can be attributed to the occurrence of droplet polymerization. 218 …”

Section: Other Methodsmentioning

confidence: 99%

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

2008

J. Polym. Sci. A Polym. Chem.

142

126

View full text Add to dashboard Cite

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.

show abstract

TEMPO‐Mediated Emulsion Polymerization

Cited by 31 publications

References 17 publications

Radical polymerization of miniemulsions induced by compressed gases

Radical polymerization of miniemulsions induced by compressed gases

Effect of stirring rate on particle formation in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene

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

Contact Info

Product

Resources

About