Living Radical Polymerization: Kinetic Results

Catala, J.‐M.; Bubel, F.; Hammouch, S. Oulad

doi:10.1021/ma00128a069

Cited by 125 publications

(89 citation statements)

References 3 publications

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“…181 However, Scheme 16 DTBN is thermally robust and has been used in NMPs. [182][183][184][185][186][187][188] One might also propose the loss of the tbutyl cation from oxammonium intermediate 65. This is also unlikely, as DTBN has been used catalytically in the oxammonium-mediated oxidations of alcohols.…”

Section: Proposed A-hydrogen Nitroxide Decomposition Mechanismmentioning

confidence: 99%

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nilsen

Braslau

2005

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:Nitroxides bearing an a-hydrogen decompose upon heating in a bimolecular reaction. A new mechanism is proposed for the decomposition of t-butylisopropylphenyl nitroxide (TIPNO) involving the formation of a head-to-tail dimer, single electron transfer to form an oxammonium salt, epimerization to the corresponding nitrone, and elimination to form a conjugated oxime. This mechanism may provide insights into designing new nitroxides for use in controlled polymerization.

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Section: Proposed A-hydrogen Nitroxide Decomposition Mechanismmentioning

confidence: 99%

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nilsen

Braslau

2005

J. Polym. Sci. A Polym. Chem.

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“…PN K kd kc P* + N* (1) In 1995 Catala et al [4] first reported the independence of polymerization rate R p on the concentration of PN. Fukuda et al have interpreted this observation by means of stationary-state kinetics [5,6] and suggested Equation (2),…”

Section: Introductionmentioning

confidence: 99%

Acetic Anhydride - Accelerating Agent for Nitroxide-Controlled Free-Radical Copolymerization of Styrene and Acrylonitrile

Baumann

Schmidt‐Naake²

2001

Macromol. Chem. Phys.

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The stereoselective hydrogenation of oxazolidinone‐substituted pyridines shown in the cover picture gives piperidines containing up to four new stereocenters. One of the biologically active compounds readily accessible by this method is (S)‐coniine, the poisonous hemlock alkaloid used in ancient Greece for executions. The famous painting by David shows Socrates shortly before drinking from the poison chalice. F. Glorius et al. describe this synthetic method on pages 2850 ff.

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“…In both cases the alkoxyamine concentration was set to [N] ¼ 0.008 M. For BB3 with N br ¼ 4.9 this equals a polymer concentration of [MI] ¼ 0.0016 M. As expected both reactions proceeded equally since the rate of an SFRP is only governed by the thermal polymerization. [23] The development of the polydispersities and molecular weights with conversion are plotted in Figure 3. Both plots are significantly higher than in the comparative linear polymerization.…”

Section: Graft Reactionmentioning

confidence: 99%

Nitroxide‐Controlled Grafting by an Insertion Mechanism using a Polymerizable N‐Oxyl

Appelt

Schmidt‐Naake

2004

Macro Materials & Eng

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Summary: The polymerizable nitroxide 4‐acryloyloxy‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl (AOTEMPO) was utilized in a two step polymerization to prepare alkoxyamine‐functionalized backbone polymers. These backbones were then used as initiators for stable free‐radical graft polymerizations in bulk at 125 °C. The products were cleaved into their linear components by reaction with L‐(+)‐ascorbic acid allowing a reproducible analysis of the molecular weights. The influences of the backbone concentration and the graft density on the polymerization were investigated. Graft polymers purely consisting of styrene were produced as well as polymers with a backbone based on 2‐ethoxyethyl acrylate (EOEA). In addition a graft polymer with block copolymer side chains was prepared by extending a preformed graft polymer. In all cases the controlled course of the reaction was confirmed by the linear increase of the molecular weights over conversion and the low polydispersities of the products.Structure of an extended graft copolymer.imageStructure of an extended graft copolymer.

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Living Radical Polymerization: Kinetic Results

Cited by 125 publications

References 3 publications

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Acetic Anhydride - Accelerating Agent for Nitroxide-Controlled Free-Radical Copolymerization of Styrene and Acrylonitrile

Nitroxide‐Controlled Grafting by an Insertion Mechanism using a Polymerizable N‐Oxyl

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