Well-Defined Random Copolymers by a “Living” Free-Radical Polymerization Process

Hawker, Craig J.; Elce, Edmund; Dao, Julian; Volksen, Willi; Russell, Thomas P.; Barclay, George G.

doi:10.1021/ma9515137

Cited by 208 publications

(194 citation statements)

References 10 publications

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“…Two-component initiating systems, which usually consist of a thermal initiator of dibenzoyl peroxide and a stable nitroxyl radical 15 or unimolecular systems incorporating nitroxide and initiating groups in 1 : 1 stoichiometry, 22,23 are usually used for controlled stable free-radical polymerization. Nitroxide-mediated pseudoliving radical polymerization in the absence of added initiating systems also seems to be a promising method.…”

Section: Introductionmentioning

confidence: 99%

Poly(styrene-co-N-butylmaleimide) macroinitiators by controlled autopolymerization and related block copolymers

Lokaj

Vl?ek

K?�?

1999

J. Appl. Polym. Sci.

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Autopolymerization of styrene-N-butylmaleimide mixtures at 125 or 140°C in the presence of a stable nitroxyl radical [2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO)] was found to proceed in a pseudoliving manner. Unimolecular initiators, which were originated by trapping self-generated radical species with TEMPO, took part in the process. Under the studied experimental conditions, the TEMPO-controlled autopolymerization with a varying comonomer ratio provided virtually alternating copolymers of narrow molecular weight distributions. The molecular weights of the copolymers increased with conversions. The obtained styrene-N-butylmaleimide copolymers containing TEMPO end groups were used to initiate the polymerization of styrene. The polymerization yielded poly(styrene-co-N-butylmaleimide)-polystyrene block copolymers with various polystyrene chain lengths and narrow molecular weight distributions. The compositions, molecular weights, and molecular weight distributions of the synthesized block copolymers and the initial poly(styrene-co-N-butylmaleimide) precursors were evaluated using nitrogen analysis, gel permeation chromatography, and 1 H-and 13 C-NMR spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Poly(styrene-co-N-butylmaleimide) macroinitiators by controlled autopolymerization and related block copolymers

Lokaj

Vl?ek

K?�?

1999

J. Appl. Polym. Sci.

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“…), composition of the backbone (i.e., random, gradient, or block co-polymer) and inclusion of functionality (i.e., chain-end, site-specific, etc.) can all be readily manipulated using living free radical methodologies while still retaining a high degree of control over the molecular weight and polydispersity [7][8][9][10][11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

“…However, there are some limitations of nitroxide-mediated procedures: their incompatibility with many vinyl monomer families [18], laborious synthesis of starting alkoxyamines [19] and high temperatures required for polymerisation [3][4][5][6]. The first problem was solved by the development of the phosphonate derivative DEPN (diethylphosphonic acid esther nitroxide, Scheme 1) by Gnanou and Tordo [20] and the work of Hawker and others [7][8][9][10][11][12][13][14][15][16][17] based on the extensive variation of the structure 2.…”

Section: Introductionmentioning

confidence: 99%

New Alkoxyamines for Controlled Radical Polymerisations

Thiessen

Wolff

2008

Designed Monomers and Polymers

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A variety of different alkoxyamine structures, which led to a new class of nitroxides with a quarternary phosphonic acid (and its ethylesther) group, was investigated. These compounds were able to control the polymerisation of styrene at temperatures as low as 70 • C. The new alkoxyamines were also tested in the polymerisation of 1-vinylimidazole. Furthermore, it was found that the free phosphonic acid can control the polymerisation of styrene assisted by microwaves. This is not possible with any other alkoxyamine. The obtained kinetic data of the microwave-assisted NMRP prove that the polymerisation proceeds in a controlled fashion and faster then the thermal analogue.  Koninklijke Brill NV, Leiden, 2008

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“…[1][2][3][4][5][6][7] These approaches have also been used in the simultaneous copolymerization of vinyl monomers to form statistical copolymers. TEMPOmediated simultaneous copolymerizations of styrene with N-vinylcarbazole, 8 styrene with chloromethylstyrene, 9 styrene with methyl methacrylate (MMA) and n-butyl acrylate (BA), 10 styrene with acrylonitrile, 11 and styrene with N-cyclohexylmaleimide (NCMI) 12 have been reported. Another important method for the controlled radical polymerization, atom transfer radical polymerization (ATRP), which was first reported by Matyjaszewski et al 1 and Sawamoto et al, 2 was also employed to copolymerize styrene with BA, 13 MMA with BA, 14 styrene with MMA, 15 styrene with bicyclic olefins, 16 and MMA with n-butyl methacrylate.…”

Section: Introductionmentioning

confidence: 99%