Compartmentalization in NMP in Dispersed Systems: Relative Contributions of Confined Space Effect and Segregation Effect Depending on Nitroxide Type

Zetterlund, Per B.; Okubo, Masayoshi

doi:10.1002/mats.200900006

Cited by 34 publications

(43 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Smaller k 2 /k t means bimolecular termination is significant, forming a larger number of trapping agents faster. Significant bimolecular termination is not suitable for the controlled RDRP, however, k 2 /k t -value as small as 1.24 × 10 −3 is reported for 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxy (TIPNO)/styrene system [29]. Figure 12 shows that the acceleration is significant for smaller k 2 /k t -values.…”

Section: Figure 12mentioning

confidence: 99%

Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization

Tobita

2011

Polymers

View full text Add to dashboard Cite

Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression,. Unique miniemulsion polymerization kinetics of RDRP are elucidated on the basis of the following two factors: (1) A high single molecule concentration in a nano-sized particle; and (2) a significant statistical concentration variation among particles. The characteristic particle diameters below which the polymerization rate start to deviate significantly (1) from the corresponding bulk polymerization, and (2) from the estimate using the average concentrations, can be estimated by using simple equations. For stable-radical-mediated polymerization (SRMP) and atom-transfer radical polymerization (ATRP), an acceleration window is predicted for the particle diameter range, ,T p ,T. For reversible-addition-fragmentation chain-transfer polymerization (RAFT), degenerative-transfer radical polymerization (DTRP) and also for the conventional nonliving radical polymerization, a significant rate increase occurs for ,R• . On the other hand, for p ,M the polymerization rate is suppressed because of a large statistical variation of monomer concentration among particles.

show abstract

Section: Figure 12mentioning

confidence: 99%

Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization

Tobita

2011

Polymers

View full text Add to dashboard Cite

show abstract

“…CLRP in dispersed systems14, 15 can under certain circumstances be strongly influenced by the phenomenon of compartmentalization, which refers to the physical isolation of reactants in discrete confined spaces, i.e., the monomer droplets or polymer particles. Effects of compartmentalization have been predicted theoretically for NMP,16–24 atom transfer radical polymerization (ATRP),22, 25–28 and reversible addition‐fragmentation chain transfer (RAFT) polymerization,21, 22, 29–32 and experimental evidence is also starting to emerge 33–36. There are two possible distinct effects of compartmentalization: The segregation effect and the confined space effect 14, 18.…”

Section: Introductionmentioning

confidence: 99%

“…The confined space effect refers to how the rate of reaction between two species is higher in a small particle than in a large particle. The confined space effect can cause the rate of deactivation to increase in CLRP systems based on the persistent radical effect (e.g., NMP and ATRP) 18–21, 23–28, 36…”

Section: Introductionmentioning

confidence: 99%

Nitroxide‐Mediated Radical Polymerization of Butyl Acrylate Using TEMPO: Improvement of Control Exploiting Nanoreactors?

Zetterlund

2010

Macro Reaction Engineering

Self Cite

View full text Add to dashboard Cite

Compartmentalization effects in the nitroxide‐mediated radical polymerization of butyl acrylate in a dispersed system using the nitroxide 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) at 130 °C have been examined by means of modeling and simulations employing modified Smith–Ewart equations that account for compartmentalization effects on both propagating radicals and free nitroxide species. TEMPO‐mediated acrylate polymerization is known to be problematic, speculated to be mainly related to excessive accumulation of free TEMPO with increasing conversion. The present theoretical results indicate that it may be possible to at least partially overcome this difficulty by careful exploitation of compartmentalization effects in nanoreactors.

show abstract

“…Their compartmentalization model, however, was not able to compute the MWD or its averages. In a later work [114], they compared the performance of two mediating agents, TEMPO and TIPNO, on the compartmentalization and livingness of the system. They found that the nature of the nitroxide influenced the minimum particle size beyond which compartmentalization could not be neglected.…”

Section: Nmp In Heterogeneousmentioning

confidence: 99%

Deterministic Approaches for Simulation of Nitroxide-Mediated Radical Polymerization

Asteasuain

2018

International Journal of Polymer Science

View full text Add to dashboard Cite

Since its development in the last decades, controlled radical polymerization (CRP) has become a very promising option for the synthesis of polymers with controlled structure. The design and production of tailor-made materials can be significantly improved by developing models capable of predicting the polymer properties from the operating conditions. Nitroxide-mediated polymerization (NMP) was the first of the three main variants of CRP to be discovered. Although it has lost preference over the years against other CRP alternatives, NMP is still an attractive synthesis method because of its simple experimental implementation and environmental friendliness. This review focuses on deterministic methods employed in mathematical models of NMP. It presents an overview of the different techniques that have been reported for modelling NMP processes in homogeneous and heterogeneous media, covering from the prediction of average properties to the latest techniques for modelling univariate and multivariate distributions of polymer properties. Finally, an outlook of model-based design studies of NMP processes is given.

show abstract

Compartmentalization in NMP in Dispersed Systems: Relative Contributions of Confined Space Effect and Segregation Effect Depending on Nitroxide Type

Cited by 34 publications

References 31 publications

Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization

Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization

Nitroxide‐Mediated Radical Polymerization of Butyl Acrylate Using TEMPO: Improvement of Control Exploiting Nanoreactors?

Deterministic Approaches for Simulation of Nitroxide-Mediated Radical Polymerization

Contact Info

Product

Resources

About