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Self-assembly of block copolymer-based ionic supramolecules based upon multi-tail amphiphiles

Asad Ayoubi, Mehran LU ; Almdal, K.; Zhu, K.; Nystrom, B.; Olsson, Ulf LU and Piculell, Lennart LU (2015) In RSC Advances 5(39). p.31091-31103
Abstract
Utilising simple acid-base titration chemistry, a new family of Linear-b-Amphiphilic Comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] featuring multi-tail side-chains have been synthesized and examined by synchrotron SAXS. To three different parent diblock copolymers of poly(styrene)-b-poly( methacrylic acid) PS-b-PMAA multi-tail ammonium side-chains of (C8)(2)-, (C8)(4) -or (C12)(2)-type were attached at various side-chain grafting densities (X), making it possible to separate effects of the details of the AC-block architecture from effects of the overall volume fraction of the AC block. The micro-segregated morphologies of these systems include AC-block filled spherical microdomains in a liquid-like state (SPHLL),... (More)
Utilising simple acid-base titration chemistry, a new family of Linear-b-Amphiphilic Comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] featuring multi-tail side-chains have been synthesized and examined by synchrotron SAXS. To three different parent diblock copolymers of poly(styrene)-b-poly( methacrylic acid) PS-b-PMAA multi-tail ammonium side-chains of (C8)(2)-, (C8)(4) -or (C12)(2)-type were attached at various side-chain grafting densities (X), making it possible to separate effects of the details of the AC-block architecture from effects of the overall volume fraction of the AC block. The micro-segregated morphologies of these systems include AC-block filled spherical microdomains in a liquid-like state (SPHLL), AC-block filled hexagonally-packed cylinders (CYL), alternating lamellar microlayers of AC- and L-blocks (LAM) and L-block filled hexagonally-packed cylinders (CYL*). For systems with the same parent diblock copolymer that also carry a constant volume fraction of AC-blocks, an increase in the side-chain length (l(sc)) and/or in the number of alkyl tails at a side-chain branch point (m) result in a microdomain morphology that is either unchanged or changed into one with a less curved interface. For lamellae-forming L-b-AC ionic supramolecules made up of the same parent diblock copolymer, a body of experimental data showing small variations in the repeat distance of the LAM micro-segregated structure (d(LAM)) could be obtained by making appropriate combinations of X, lsc and m. For such lamellae-forming L-b-AC ionic supramolecules, the average of d(LAM) values decreases when l(sc) and/or m increase. For systems with (C12)(2)-type side-chains, the effective Flory-Huggins interaction parameter between L-and AC-blocks chi'(C12)(2)/X was determined at various side-chain grafting densities and it was observed that chi'(C12)(2)/X increases when X is increased. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
RSC Advances
volume
5
issue
39
pages
31091 - 31103
publisher
Royal Society of Chemistry
external identifiers
  • wos:000352791300084
  • scopus:84926665149
ISSN
2046-2069
DOI
10.1039/c5ra03220b
language
English
LU publication?
yes
id
e6cfc1da-daa5-4591-b3cd-7eff557365d3 (old id 5401180)
date added to LUP
2015-05-19 11:12:03
date last changed
2017-01-01 05:38:31
@article{e6cfc1da-daa5-4591-b3cd-7eff557365d3,
  abstract     = {Utilising simple acid-base titration chemistry, a new family of Linear-b-Amphiphilic Comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] featuring multi-tail side-chains have been synthesized and examined by synchrotron SAXS. To three different parent diblock copolymers of poly(styrene)-b-poly( methacrylic acid) PS-b-PMAA multi-tail ammonium side-chains of (C8)(2)-, (C8)(4) -or (C12)(2)-type were attached at various side-chain grafting densities (X), making it possible to separate effects of the details of the AC-block architecture from effects of the overall volume fraction of the AC block. The micro-segregated morphologies of these systems include AC-block filled spherical microdomains in a liquid-like state (SPHLL), AC-block filled hexagonally-packed cylinders (CYL), alternating lamellar microlayers of AC- and L-blocks (LAM) and L-block filled hexagonally-packed cylinders (CYL*). For systems with the same parent diblock copolymer that also carry a constant volume fraction of AC-blocks, an increase in the side-chain length (l(sc)) and/or in the number of alkyl tails at a side-chain branch point (m) result in a microdomain morphology that is either unchanged or changed into one with a less curved interface. For lamellae-forming L-b-AC ionic supramolecules made up of the same parent diblock copolymer, a body of experimental data showing small variations in the repeat distance of the LAM micro-segregated structure (d(LAM)) could be obtained by making appropriate combinations of X, lsc and m. For such lamellae-forming L-b-AC ionic supramolecules, the average of d(LAM) values decreases when l(sc) and/or m increase. For systems with (C12)(2)-type side-chains, the effective Flory-Huggins interaction parameter between L-and AC-blocks chi'(C12)(2)/X was determined at various side-chain grafting densities and it was observed that chi'(C12)(2)/X increases when X is increased.},
  author       = {Asad Ayoubi, Mehran and Almdal, K. and Zhu, K. and Nystrom, B. and Olsson, Ulf and Piculell, Lennart},
  issn         = {2046-2069},
  language     = {eng},
  number       = {39},
  pages        = {31091--31103},
  publisher    = {Royal Society of Chemistry},
  series       = {RSC Advances},
  title        = {Self-assembly of block copolymer-based ionic supramolecules based upon multi-tail amphiphiles},
  url          = {http://dx.doi.org/10.1039/c5ra03220b},
  volume       = {5},
  year         = {2015},
}