Polyacrylonitrile-containing amphiphilic block copolymers: self-assembly and porous membrane formation

Lea Gemmer; Bart-Jan Niebuur; Christian Dietz; Daniel Rauber; Martina Plank; Florian V. Frieß; Volker Presser; Robert W. Stark; Tobias Kraus; Markus Gallei

doi:10.1039/D3PY00836C

Polyacrylonitrile-containing amphiphilic block copolymers: self-assembly and porous membrane formation†

Lea Gemmer,^a Bart-Jan Niebuur,

^b Christian Dietz,

^c Daniel Rauber,

^d Martina Plank,^e Florian V. Frieß,^a Volker Presser,

^dfg Robert W. Stark,

^c Tobias Kraus

^bh and Markus Gallei

*^ag

Author affiliations

* Corresponding authors

^a Polymer Chemistry, Universität des Saarlandes, Campus C4 2, 66123 Saarbrücken, Germany
E-mail: markus.gallei@uni-saarland.de

^b INM – Leibniz-Institute for New Materials, Campus D2 2, 66123 Saarbrücken, Germany

^c Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Peter-Grünberg-Straße 2, 64287 Darmstadt, Germany

^d Department of Materials Science and Engineering, Saarland University, 66123 Saarbrücken, Germany

^e Ernst-Berl Institute of Technical and Macromolecular Chemistry, Technische Universität Darmstadt, Peter-Grünberg-Straße 4, 64287 Darmstadt, Germany

^f INM - Leibniz-Institute for New Materials, Campus D2 2, 66123 Saarbrücken, Germany

^g Saarene, Saarland Center for Energy Materials and Sustainability, Campus C4 2, 66123 Saarbrücken, Germany

^h Colloid and Interface Chemistry, Universität des Saarlandes, Campus D2 2, 66123 Saarbrücken, Germany

Abstract

The development of hierarchically porous block copolymer (BCP) membranes via the application of the self-assembly and non-solvent induced phase separation (SNIPS) process is one important achievement in BCP science in the last decades. In this work, we present the synthesis of polyacrylonitrile-containing amphiphilic BCPs and their unique microphase separation capability, as well as their applicability for the SNIPS process leading to isoporous integral asymmetric membranes. Poly(styrene-co-acrylonitrile)-b-poly(2-hydroxyethyl methacrylate)s (PSAN-b-PHEMA) are synthesized via a two-step atom transfer radical polymerization (ATRP) procedure rendering PSAN copolymers and BCPs with overall molar masses of up to 82 kDa while maintaining low dispersity index values in the range of Đ = 1.13–1.25. The polymers are characterized using size-exclusion chromatography (SEC) and NMR spectroscopy. Self-assembly capabilities in the bulk state are examined using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) measurements. The fabrication of isoporous integral asymmetric membranes is investigated, and membranes are examined by scanning electron microscopy (SEM). The introduction of acrylonitrile moieties within the membrane matrix could improve the membranes’ mechanical properties, which was confirmed by nanomechanical analysis using atomic force microscopy (AFM).

Polymer Chemistry

Polyacrylonitrile-containing amphiphilic block copolymers: self-assembly and porous membrane formation†

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Polyacrylonitrile-containing amphiphilic block copolymers: self-assembly and porous membrane formation

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