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Nanostructured proton conducting polystyrene - poly(vinylphosphonic acid) block copolymers prepared via sequential anionic polymerizations

Perrin, Renaud LU ; Elomaa, Matti and Jannasch, Patric LU (2009) In Macromolecules 42(14). p.5146-5154
Abstract
Poly(styrene-b-vinylphosphonic acid) diblock copolymers have been prepared via sequential anionic polymerization and evaluated as nanostructured polymer electrolytes. The ionic block copolymers were synthesized by first initiating the polymerization of styrene using n-butyllithium in tetrahydrofuran at −78 °C. 1,1-Diphenylethylene was then added to the living polystyryl anions before charging diethyl vinylphosphonate to polymerize the second block. The poly(diethyl phosphonate) block was subsequently completely hydrolyzed to obtain the poly(vinylphosphonic acid) block. Analysis by calorimetry showed two distinct glass transitions of the acidic copolymers, indicating phase separation between the two blocks. The glass transition temperature... (More)
Poly(styrene-b-vinylphosphonic acid) diblock copolymers have been prepared via sequential anionic polymerization and evaluated as nanostructured polymer electrolytes. The ionic block copolymers were synthesized by first initiating the polymerization of styrene using n-butyllithium in tetrahydrofuran at −78 °C. 1,1-Diphenylethylene was then added to the living polystyryl anions before charging diethyl vinylphosphonate to polymerize the second block. The poly(diethyl phosphonate) block was subsequently completely hydrolyzed to obtain the poly(vinylphosphonic acid) block. Analysis by calorimetry showed two distinct glass transitions of the acidic copolymers, indicating phase separation between the two blocks. The glass transition temperature of the densely phosphonated blocks was strongly influenced by the formation of anhydride links through reversible self-condensation reactions at elevated temperatures. Studies of thin copolymer films by tapping mode atomic force microscopy revealed nanophase-separated morphologies with continuous phosphonated domains. In addition, the acidic block copolymers were found to self-assemble into spherical micellar nanoparticles which, in turn, formed branched arrays of supramolecular “necklace-like” chain structures. Block copolymers equilibrated at 25 °C and 98% relative humidity reached proton conductivities in the order of 30 mS/cm at 130 °C. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Macromolecules
volume
42
issue
14
pages
5146 - 5154
publisher
The American Chemical Society
external identifiers
  • wos:000268175800033
  • scopus:67651093819
ISSN
0024-9297
DOI
10.1021/ma900703j
language
English
LU publication?
yes
id
7c6fea9a-aaee-4677-8d9e-7a0e8985a7a3 (old id 1398186)
alternative location
http://pubs.acs.org/doi/abs/10.1021/ma900703j?
date added to LUP
2009-06-23 14:37:54
date last changed
2017-10-01 03:49:37
@article{7c6fea9a-aaee-4677-8d9e-7a0e8985a7a3,
  abstract     = {Poly(styrene-b-vinylphosphonic acid) diblock copolymers have been prepared via sequential anionic polymerization and evaluated as nanostructured polymer electrolytes. The ionic block copolymers were synthesized by first initiating the polymerization of styrene using n-butyllithium in tetrahydrofuran at −78 °C. 1,1-Diphenylethylene was then added to the living polystyryl anions before charging diethyl vinylphosphonate to polymerize the second block. The poly(diethyl phosphonate) block was subsequently completely hydrolyzed to obtain the poly(vinylphosphonic acid) block. Analysis by calorimetry showed two distinct glass transitions of the acidic copolymers, indicating phase separation between the two blocks. The glass transition temperature of the densely phosphonated blocks was strongly influenced by the formation of anhydride links through reversible self-condensation reactions at elevated temperatures. Studies of thin copolymer films by tapping mode atomic force microscopy revealed nanophase-separated morphologies with continuous phosphonated domains. In addition, the acidic block copolymers were found to self-assemble into spherical micellar nanoparticles which, in turn, formed branched arrays of supramolecular “necklace-like” chain structures. Block copolymers equilibrated at 25 °C and 98% relative humidity reached proton conductivities in the order of 30 mS/cm at 130 °C.},
  author       = {Perrin, Renaud and Elomaa, Matti and Jannasch, Patric},
  issn         = {0024-9297},
  language     = {eng},
  number       = {14},
  pages        = {5146--5154},
  publisher    = {The American Chemical Society},
  series       = {Macromolecules},
  title        = {Nanostructured proton conducting polystyrene - poly(vinylphosphonic acid) block copolymers prepared via sequential anionic polymerizations},
  url          = {http://dx.doi.org/10.1021/ma900703j},
  volume       = {42},
  year         = {2009},
}