NDLI: Micro- and nanophase separations in hierarchical self-assembly of strongly amphiphilic block copolymer-based ionic supramolecules

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Micro- and nanophase separations in hierarchical self-assembly of strongly amphiphilic block copolymer-based ionic supramolecules

Content Provider	Royal Society of Chemistry (RSC)
Author	Nyström, Bo Piculell, Lennart Olsson, Ulf Almdal, Kristoffer Ayoubi, Mehran Asad Zhu, Kaizheng
Copyright Year	2013
Abstract	By a selective complexation between different alkyltrimethylammonium amphiphiles (C8, C12 and C16) and three different diblock copolymer systems of poly(styrene)-b-poly(methacrylic acid) at various grafting densities X (X = number of alkyl chains per acidic group of the poly(methacrylic acid) PMAA block), a class of ionic supramolecules are successfully synthesized whose molecular architecture consists of a poly(styrene) PS block (Linear block) covalently connected to a strongly amphiphilic comb-like block (AmphComb block), i.e. Linear-b-AmphComb. In the melt state, these ionic supramolecules can show simultaneous microphase (between Linear and AmphComb blocks) and nanophase (within the AmphComb blocks) separations. This leads to the formation of various structure-in-structure two-scale hierarchical self-assemblies, including S-in-SLL, S-in-SBCC, S-in-C, S-in-L and C-in-L, where S, SLL, SBCC, C and L stand for spherical, spherical in liquid-like state, spherical in body-centered-cubic arrangement, cylindrical and lamellar, respectively. Synchrotron small angle X-ray scattering (SAXS) and crossed polarizers, together with SAXS modelling analysis, were used for a detailed structural study of the samples. The morphology of the microphase separated state was mapped out on ‘master’ microdomain morphology diagrams as a function of the volume fraction of the AmphComb blocks (ΦAmphComb) and the compositional window of each microdomain morphology was determined. It was observed that, (i) within samples based on the same parent diblock copolymer system, the occurrence of a specific microdomain morphology is only dependent on the value of ΦAmphComb, regardless of the grafting density X and the length of the alkyl side-chains, and (ii) microdomain morphological boundaries occur at ΦAmphComb values of ∼0.20 (SLL/C and SBCC/C) and ∼0.28 (C/L). Finally, the specific influences of the strongly amphiphilic nature of the AmphComb blocks on the observed morphological and hierarchical behaviours of our system are discussed. For reference, stoichiometric strongly amphiphilic comb-like (AmphComb) ionic supramolecules, based on complexation between a homopolymer of PMAA and the various alkyltrimethylammonium amphiphiles, were prepared, which nanophase separated into S (C8) or C (C12 and C16) domains.
Starting Page	1540
Ending Page	1555
Page Count	16
File Format	HTM / HTML PDF
ISSN	1744683X
Volume Number	9
Issue Number	5
Journal	Soft Matter
DOI	10.1039/c2sm27113c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Stoichiometry Poly(methacrylic acid) SBCC Polymer Nanophase material Grafting Small-angle X-ray scattering Carboxylic acid Styrene Alkane PMAA Amphiphile Copolymer Crystal structure
Content Type	Text
Resource Type	Article
Subject	Chemistry Condensed Matter Physics

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