Poly(n-butyl acrylate) Homopolymer and Poly[n-butyl acrylate-b-(n-butyl acrylate-co-styrene)] Block Copolymer Prepared via Nitroxide-Mediated Living/Controlled Radical Polymerization in Miniemulsion

Farcet, Céline; Charleux, Bernadette; Pirri, Rosangela

doi:10.1021/ma010011s

Cited by 79 publications

(62 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Such polymers have potential application in the fabrication of commercially valuable block copolymers, [1,2] drug delivery systems, [3] nanotechnology, [4] adhesives, surfactants, and polymer compatibilizers. The distinguishing feature of NMP is the use of a nitroxide, such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), to reversibly deactivate active polymer radicals to give a dormant alkoxyamine molecule (see Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Interfacial Mass Transfer in Nitroxide-Mediated Miniemulsion Polymerization

John

Cunningham

McAuley

et al. 2002

Macromol. Theory Simul.

View full text Add to dashboard Cite

A mathematical model has been developed to describe the interfacial mass transfer of TEMPO in a nitroxide‐mediated miniemulsion polymerization (NMMP) system in the absence of chemical reactions. The model is used to examine how the diffusivity of TEMPO in the aqueous and organic droplet phases, the average droplet diameter and the nitroxide partition coefficient influences the time required for the nitroxide to reach phase equilibrium under non‐steady state conditions. Our model predicts that phase equilibrium is achieved quickly (< 1 × 10−4 s) in NMMP systems under typical polymerization conditions and even at high monomer conversions when there is significant resistance to molecular diffusion. The characteristic time for reversible radical deactivation by TEMPO was found to be more than ten times greater than the predicted equilibration times, indicating that phase equilibrium will be achieved before TEMPO has an opportunity to react with active polymer radicals. However, significantly longer equilibration times are predicted, when average droplet diameters are as large as those typically found in emulsion and suspension polymerization systems, indicating that the aqueous and organic phase concentrations of nitroxide may not always be at phase equilibrium during polymerization in these systems.

show abstract

Section: Introductionmentioning

confidence: 99%

Interfacial Mass Transfer in Nitroxide-Mediated Miniemulsion Polymerization

John

Cunningham

McAuley

et al. 2002

Macromol. Theory Simul.

View full text Add to dashboard Cite

show abstract

“…TEMPO is the most widely used nitroxide and mainly applied for the controlled polymerization of styrenic monomer at T > 120 • C. Farcet et al [28] developed a new generation of acyclic β-phosphonylated nitroxides that are efficient at lower temperatures, not only for the polymerization of styrene, but also for that of alkylacrylates, acrylamides, dienes, etc. N-tert-butyl-N-(1-diethylphosphono-2, 2-dimethylpropyl) nitroxide (SG-1, Fig.…”

Section: Nitroxide-mediated Living Free-radical Polymerization (Nmrp)mentioning

confidence: 99%

Recent Research Progress in the Synthesis and Properties of Amphiphilic Block Co-polymers and Their Applications in Emulsion Polymerization

Zhou

Wang

2009

Designed Monomers and Polymers

View full text Add to dashboard Cite

Amphiphilic block co-polymers are an interesting class of polymeric surfactants. They have been used as rheology modifiers, stabilizing agents of latexes, emulsifiers, de-emulsifiers, flocculants, etc. In this paper the recent advances made in the synthesis of amphiphilic block co-polymer via controlled free-radical copolymerization are reviewed and surfactant properties of amphiphilic block co-polymers are described, such as critical micelle concentrations, surface activity, solubilization capacity of hydrophobic substances in micelles and foaming property. The effect of some parameters on the emulsion polymerization is presented, such as the composition and structure of amphiphilic block co-polymers, block length and the weight ratio of the hydrophilic and hydrophobic segments, and block co-polymer concentration.

show abstract

“…In particular the side reactions are bimolecular terminations by combination, Equation (4), or disproportionation, Equation (5), of two transient radicals (P n * and P m *), or terminations by reactions between the transient and the persistent radical which can either occur as elimination in the dormant state, Equation (6), or disproportionation between the dissociated radicals, Equation (7). Reactions (4) and (5) lead to a loss of propagating radicals and to a build-up of free nitroxide, whereas reactions (6) and (7) by the formation of unsaturated chain ends and hydroxyl amine cause a loss of propagating radicals and nitroxide radicals, too.…”

Section: Controlled Radical Copolymerizations Of Styrene and Acrylatesmentioning

confidence: 99%

“…[1,2] Beside the syntheses of well-defined polymer architectures, especially the controlled copolymerizations of styrene with methacrylates and acrylates have been thoroughly investigated. [3][4][5][6][7] These systems provide the opportunity to modify product properties such as glass transition temperature, polymer compatibility and solubility.…”

Section: Introductionmentioning

confidence: 99%

Stable Free‐Radical Copolymerization of Styrene with Acrylates Using OH‐TEMPO

Appelt

Schmidt‐Naake

2004

Macro Chemistry & Physics

View full text Add to dashboard Cite

Summary: Stable free‐radical copolymerizations (SFRP) of styrene with N‐acryloyl morpholine (AMo), 2‐ethoxyethyl acrylate (EOEA) and isobornyl acrylate (iBoA), respectively, were carried out under control of the stable nitroxide radical 4‐hydroxy‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl (OH‐TEMPO). The polymerizations were initiated by a polystyrene macroinitiator (PS‐MI). No accelerating agents were used. In contrast to the experiences made with methacrylates there was no decrease in the polymerization rates up to 50 mol‐% of AMo or EOEA in the monomer mixture. This behavior was ascribed to a compensation of the lack of thermal initiation by the high propagation rate constants of the acrylates. The produced AB diblock polymers were successfully employed in block extension reactions in styrene yielding ABA triblock polymers. Copolymerization reactivity ratios (r‐values) and glass transition temperatures have been estimated.Monomer structures.magnified imageMonomer structures.

show abstract

Poly(n-butyl acrylate) Homopolymer and Poly[n-butyl acrylate-b-(n-butyl acrylate-co-styrene)] Block Copolymer Prepared via Nitroxide-Mediated Living/Controlled Radical Polymerization in Miniemulsion

Cited by 79 publications

References 28 publications

Interfacial Mass Transfer in Nitroxide-Mediated Miniemulsion Polymerization

Interfacial Mass Transfer in Nitroxide-Mediated Miniemulsion Polymerization

Recent Research Progress in the Synthesis and Properties of Amphiphilic Block Co-polymers and Their Applications in Emulsion Polymerization

Stable Free‐Radical Copolymerization of Styrene with Acrylates Using OH‐TEMPO

Contact Info

Product

Resources

About