One-step synthesis of alkoxyamines for nitroxide-mediated radical polymerization

Grubbs, Robert B.; Wegrzyn, Jakub K.; Xia, Qing

doi:10.1039/b413358g

Cited by 49 publications

(51 citation statements)

References 14 publications

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“…Later on, more active acyclic nitroxides containing an α-hydrogen, such as DEPN (N-tert-butyl-N-(1-di-ethylphosphono-2,2-dimethylpropyl)-N-oxyl) [11][12][13][14][15][16][17] and TIPNO (2,2,5,5-tetramethyl-4-phenyl-3-azahexane-3-oxyl) [18] and [19], were developed with great success in the controlled radical polymerization of a broader range of monomers, including styrene and derivatives, acrylates, acrylamide, acrylonitrile, acrylic acid and dienes. Recently, an alkoxyamine derived from TIPNO was prepared in one-step [20] and used in the controlled radical polymerization of styrene and isoprene at 125 °C. The radical polymerization of acrylates did not fall under control with this alkoxyamine.…”

Section: Introductionmentioning

confidence: 99%

Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides

Sciannamea

Guerrero‐Sánchez

Schubert

et al. 2005

Polymer

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The ability of several nitrones to control the radical polymerization of styrene at 110 °C has been investigated by high-throughput experimentation. The nitrone/free radical initiator pair dictates the structure of the nitroxide and the alkoxyamine formed in situ, which determines the position of the equilibrium between the active and the dormant species operating in the nitroxide-mediated polymerization. For the styrene polymerization to be controlled, the nitrone must be reacted with 2,2′-azo-bis-isobutyronitrile (AIBN) at 85 °C, prior to addition of styrene and polymerization at 110 °C. The effect of the nitrone structure on the kinetics of the styrene polymerization has been emphasized. Amongst all the nitrones tested, those of the C-phenyl-N-tert-butylnitrone (PBN) type are the most efficient in terms of polymerization rate, control of molecular weight and polydispersity. Electrophilic substitution of the phenyl group of PBN by either an electrodonor or an electroacceptor group has only a minor effect on the polymerization kinetics. Importantly, the polymerization rate is not governed by the thermal polymerization of styrene but by the alkoxyamine formed in situ during the pre-reaction step. The initiation efficiency is, however, very low, consistent with a limited conversion of the nitrone into nitroxide and alkoxyamine.

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Section: Introductionmentioning

confidence: 99%

Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides

Sciannamea

Guerrero‐Sánchez

Schubert

et al. 2005

Polymer

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“…The hyperfine coupling constants of the radical produced from 2 (a P ¼ 46.2 G; a N ¼ 13.6 G) are fully consistent with those of the known nitroxide SG1 radical. [31] The radical formed in 3 (g % 2.006; a N ¼ 14.7 G; a H ¼ 3.2 G) can also be assigned to a nitroxide and has similar hyperfine coupling constants than the nitroxide developed by Grubbs, [32,33] where the BP group is replaced by a phenyl group. In the same experimental conditions, due to the low UV absorption of 1 or 1(, the ESR experiments do not reveal a noticeable formation of nitroxide.…”

Section: Instrumentationmentioning

confidence: 98%

Photodissociation Rate Constants of New Light Sensitive Alkoxyamines

Versace

Lalevée

Fouassier

et al. 2010

Macromol. Rapid Commun.

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The photochemical properties of two new photocleavable alkoxyamines bearing a benzophenone-derived chromophore were studied by electron spin resonance (ESR). The CO bond cleavage has been demonstrated and the photolysis rate constants (k(d) ) determined over a large range of light intensity through the monitoring of the nitroxide concentration in aerated conditions. The obtained kinetic data highlight for the first time the linear dependence of k(d) on the light intensity for alkoxyamines: this should be a driving factor for nitroxide mediated radical photopolymerization (NMP(2) ).

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“…Since its discovery [1,2], nitroxide mediated radical polymerization (NMRP) has been improved especially with the emergence of the nitroxides of second generation [3][4][5][6][7][8][9][10][11] whose s are versatile initiators/mediators of NMRP as they provide the control of molecular weight, polydispersity and end-group functionality during polymerization of almost all vinylic monomers polymerizable by a radical process. The C-O bond of an alkoxyamine is a relative robust bond except under strong oxidative [12], reductive conditions [13] or when it is heated during polymerization [1].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of versatile TIPNO-based alkoxyamines

Marx

Eskandani

Hémery

2009

Reactive and Functional Polymers

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One-step synthesis of alkoxyamines for nitroxide-mediated radical polymerization

Abstract: An alkoxyamine that is an effective initiator for the controlled polymerization of styrene and isoprene has been prepared by the reaction of 2-methyl-2-nitrosopropane with two equivalents of radicals derived from 1-bromoethylbenzene.

Cited by 49 publications

References 14 publications

Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides

Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides

Photodissociation Rate Constants of New Light Sensitive Alkoxyamines

Synthesis of versatile TIPNO-based alkoxyamines

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