University CrestControlled-Structure Water-Soluble PolymersArmes Research Group
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Designed by Peter Iddon
Maintained by Matt Rymaruk
This Page Last Modified:
  4 September 2005

We have recently developed the use of atom transfer radical polymerisation (ATRP) in aqueous or alcoholic media for the controlled radical polymerisation of a wide range of hydrophilic methacrylates. Examples include cationic, anionic, non-ionic and betaine monomers [Y. Li et al., Macromolecules, 2003; P. D. Iddon et al., Polymer, 2004], with more recent work focusing on the direct synthesis of two new sugar methacrylates [R. Narain and S. P. Armes, Biomacromolecules, 2003] and also the design of non-linear architectures [Y. Cai and S. P. Armes, Macromolecules, 2004]

A fundamental study of the water-solubility of poly(2-hydroxyethyl methacrylate) has also recently appeared [J. V. M. Weaver et al., Macromolecules, 2004]. By preparing a series of near-monodisperse homopolymers with mean degrees of polymerisation (Dp) varying systematically from 10 to 100, three distinct solubility regimes were identified. Oligomers with Dp's < 20 were completely water-soluble regardless of the solution temperature, homopolymers with Dp's ranging from 20 to 40 were water-soluble but exhibited inverse temperature solubility behaviour (with cloud points decreasing at higher Dp), and higher molecular weight homopolymers were no longer fully water-soluble.

Derivatisation of several hydroxyl-functional methacrylic polymers using succinic anhydride under mild conditions has led to the formation of relatively hydrophobic polyacids [X. Bories-Azeau et al., Macromolecules, 2004]. This synthetic advance has proven useful for the design of new shell cross-linked micelles, 'schizophrenic' block copolymers and pigment dispersants.

Selected Publications
"Nanostructure of polyplexes formed between cationic diblock copolymer and antisense oligodeoxynucleotide and its influence on cell transfection"
X. Zhao, F. Pan, Z. Zhang, C. Grant, Y. Ma, S. P. Armes, Y. Tang, A. L. Lewis, T. Waigh, J. R. Lu
Biomacromolecules 2007, 8, 3493
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"pH-responsive behavior of selectively quaternized diblock copolymers adsorbed at the silica/aqueous solution interface"
K. Sakai, E. G. Smith, G. B. Webber, M. Baker, E. J. Wanless, V. Butun, S. P. Armes, S. Biggs
Journal of Colloid and Interface Science 2007, 314, 381
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"Probing the micellization kinetics of pyrene end-labeled diblock copolymers via a combination of stopped-flow light-scattering and fluorescence techniques"
J. Zhang, Y. Li, S. P. Armes, S. Liu
Journal of Physical Chemistry B 2007, 111, 12111
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"Autonomous volume transitions of a polybase triblock copolymer gel in a chemically driven pH-oscillator"
P. D. Topham, J. R. Howse, C. J. Crook, A. J. Gleeson, W. Bras, S. P. Armes, R. A. Jones, A. J. Ryan
Macromolecular Symposia 2007, 256, 95
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"RAFT synthesis of branched acrylic copolymers"
C. D. Vo, J. Rosselgong, S. P. Armes, N. C. Billingham
Macromolecules 2007, 40, 7119
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"Effect on salt on the micellisation kinetics of pH-responsive ABC triblock copolymers"
Z. Zhu, J. Xu, Y. Zhou, X. Jiang, S. P. Armes, S. Liu
Macromolecules 2007, 40, 6393
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"Direct synthesis and stimulus-responsive micellization of Y-shaped hydrophilic block copolymers"
Y. Cai, Y. Tang and S. P. Armes
Macromolecules 2004, 37, 9728
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"Synthesis of near-monodisperse acidic homopolymers and block copolymers from hydroxylated methacrylic copolymers using succinic anhydride under mild conditions"
X. Bories-Azeau, T. Merian, J. V. M. Weaver, S. P. Armes and H. J. W. van den Haak
Macromolecules 2004, 37, 8903
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"Stimulus-responsive water-soluble polymers based on 2-hydroxyethyl methacrylate"
J. V. M. Weaver, I. Bannister, K. L. Robinson, X. Bories-Azeau and S. P. Armes
Macromolecules 2004, 37, 2395
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"Facile synthesis of zwitterionic diblock copolymers without protecting group chemistry"
X. Bories-Azeau, S. P. Armes, and H. J. W. van den Haak
Macromolecules 2004, 37, 2348
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"Polymerization of sodium 4-styrenesulfonate via atom transfer radical polymerization in protic media"
P. D. Iddon, K. L. Robinson, and S. P. Armes
Polymer 2004, 45, 759
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"Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers"
R. Narain, S. P. Armes
Biomacromolecules 2003, 4, 1746
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"Direct synthesis of well-defined quaternized homopolymers and diblock copolymers via ATRP in protic media"
Y. Li, X. Jin, S. Zhu and S. P. Armes
Macromolecules 2003, 36, 8268
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"Direct synthesis and aqueous solution properties of well-defined cyclic sugar methacrylate polymers"
R. Narain and S. P. Armes
Macromolecules 2003, 36, 4675
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"Synthesis of controlled-structure sulfate-based copolymers via atom transfer radical polymerisation and their use as crystal habit modifiers for barium sulfate"
K. L. Robinson, J. V. M. Weaver, S. P. Armes, E. Diaz Marti, F. C. Meldrum
Journal of Materials Chemistry 2002, 12, 890
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"Atom transfer radical polymerisation of hydroxy-functional methacrylates at ambient temperature. Comparison of glycerol monomethacrylate with 2-hydroxypropyl methacrylate"
M. Save, J. V. M. Weaver, S. P. Armes, and P. McKenna
Macromolecules 2002, 35, 1152
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"Unexpected Transesterification of Tertiary Amine Methacrylates during Methanolic ATRP at Ambient Temperature: A Cautionary Tale"
X. Bories-Azeau, S. P. Armes
Macromolecules 2002, 35, 10241
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"Controlled-structure hydrophilic copolymers for the dispersion of high performance ceramics in aqueous media"
M. Vamvakaki, N. C. Billingham, S. P. Armes, J. F. Watts and S. J. Greaves
Journal of Materials Chemistry 2001, 11, 2437
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"Facile synthesis of well-defined, biocompatible phosphorylcholine-based methacrylate copolymers by atom transfer radical polymerisation at 20 °C"
E. J. Lobb, I. Ma, N. C. Billingham, S. P. Armes and A. L. Lewis
Journal of the American Chemical Society 2001, 123, 7913
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"Effect of partial quaternization on tertiary amine-based polymeric surfactants: unexpected separation of surface activity and LCST behavior"
M. Vamvakaki, G. F. Unali, V. Butun, S. Boucher, K. L. Robinson, N.C. Billingham, and S. P. Armes
Macromolecules 2001, 34, 6839
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"Controlled polymerization of 2-hydroxyethyl methacrylate by ATRP at ambient temperature"
K. L. Robinson, M. A. Khan, M. V. de Paz-Banez, X. S. Wang and S. P. Armes
Macromolecules 2001, 34, 3155
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"Selective quaternisation of tertiary amine methacrylate diblock copolymers: synthesis and aqueous solution properties"
V. Butun, N. C. Billingham and S. P. Armes
Macromolecules 2001, 34, 1148
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"Synthesis and aqueous solution properties of near-monodisperse tertiary amine methacrylate homopolymers and diblock copolymers"
V. Butun, N. C. Billingham and S. P. Armes
Polymer 2001, 42, 5993
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"pH-controlled adsorption of polyelectrolyte block copolymers at the solid/liquid interface"
D. A. Styrkas, J. L. Keddie, J. R. Lu, V. Butun and S. P. Armes
Langmuir 2000, 16, 5980
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"Facile synthesis of acidic polymers via atom transfer radical polymerisation in aqueous media at ambient temperature"
X.-S. Wang, R. A. Jackson and S. P. Armes
Macromolecules 2000, 33, 255
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"Synthesis and aqueous solution properties of novel hydrophilic-hydrophilic block copolymers"
V. Butun, M. Vamvakaki, N. C. Billingham, S. P. Armes,
Polymer 2000, 41, 3173
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"Synthesis of controlled-structure water-soluble diblock copolymers by oxyanionic polymerisation"
M. Vamvakaki, N. C. Billingham and S. P. Armes
Macromolecules 1999, 32, 2088
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"Synthesis of well-defined water-soluble statistical copolymers containing pendent ethylene glycol residues"
M. Vamvakaki, N. C. Billingham and S. P. Armes
Polymer 1999, 40, 5161
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Related Presentations
> "Atom Transfer Radical Polymerisation of 2-(Dimethylamino)ethyl Methacrylate in Protic Media at Room Temperature" [PDF; 384KB]
Macro Group 2002, Warwick
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> "Copper-Mediated Atom Transfer Radical Polymerisation (ATRP) of Acrylates in Protic Solution" [PDF; 135KB]
Macro Group 2002, Warwick
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> "Esterification of Hydroxylated Polymers with 2-Sulfobenzoic Acid Cyclic Anhydride" [PDF; 300KB]
Macro Group Young Researchers Meeting 2005, Sheffield
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> "Polymerisation of Sodium 4-Styrenesulfonate via Atom Transfer Radical Polymerisation" [PDF; 264KB]
ACS 2004, Philadelphia
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> "Unexpected Transesterification of Tertiary Amine Methacrylates During Methanolic ATRP at Ambient Temperature: A Cautionary Tale" [PDF; 364KB]
ACS 2003, New Orleans
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