TY - JOUR
T1 - Highly Tunable Nanostructures in a Doubly pH-Responsive Pentablock Terpolymer in Solution and in Thin Films
AU - Jung, Florian A.
AU - Schart, Maximilian
AU - Bührend, Lukas
AU - Meidinger, Elisabeth
AU - Kang, Jia Jhen
AU - Niebuur, Bart Jan
AU - Ariaee, Sina
AU - Molodenskiy, Dmitry S.
AU - Posselt, Dorthe
AU - Amenitsch, Heinz
AU - Tsitsilianis, Constantinos
AU - Papadakis, Christine M.
N1 - Funding Information:
The authors thank Wei Cao and Lucas P. Kreuzer (both TU München) for help with the AFM and the FTIR measurements. The PDMAEMA homopolymer sample was kindly provided by Prof. Costas S. Patrickios from the University of Patras. The authors acknowledge the CERIC‐ERIC Consortium for the access to experimental facilities and financial support. This work is based upon experiments performed at beamline P12 operated by European Molecular Biology Laboratory (EMBL), Hamburg Outstation, Deutsches Elektronen‐Synchrotron Germany. EMBL is acknowledged for beam time allocation and for providing excellent equipment and support. The authors thank Deutsche Forschungsgemeinschaft (DFG) for financial support (PA 771/19‐1). S.A. and D.P. thank DanScatt (Danish Instrument Centre for users of synchrotron‐ and neutron‐sources as well as free‐electron X‐ray lasers) and Danish Council for Independent Research Grant DFF 7014‐00288 for financial support. D.S.M. acknowledges financial support by the BMBF grant 16QK10A (SAS‐BSOFT).
Funding Information:
The authors thank Wei Cao and Lucas P. Kreuzer (both TU M?nchen) for help with the AFM and the FTIR measurements. The PDMAEMA homopolymer sample was kindly provided by Prof. Costas S. Patrickios from the University of Patras. The authors acknowledge the CERIC-ERIC Consortium for the access to experimental facilities and financial support. This work is based upon experiments performed at beamline P12 operated by European Molecular Biology Laboratory (EMBL), Hamburg Outstation, Deutsches Elektronen-Synchrotron Germany. EMBL is acknowledged for beam time allocation and for providing excellent equipment and support. The authors thank Deutsche Forschungsgemeinschaft (DFG) for financial support (PA 771/19-1). S.A. and D.P. thank DanScatt (Danish Instrument Centre for users of synchrotron- and neutron-sources as well as free-electron X-ray lasers) and Danish Council for Independent Research Grant DFF 7014-00288 for financial support. D.S.M. acknowledges financial support by the BMBF grant 16QK10A (SAS-BSOFT). Open access funding enabled and organized by Projekt DEAL.
Publisher Copyright:
© 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
PY - 2021/8/9
Y1 - 2021/8/9
N2 - Multiblock copolymers with charged blocks are complex systems that show great potential for enhancing the structural control of block copolymers. A pentablock terpolymer PMMA-b-PDMAEMA-b-P2VP-b-PDMAEMA-b-PMMA is investigated. It contains two types of midblocks, which are weak cationic polyelectrolytes, namely poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-vinylpyridine) (P2VP). Furthermore, these are end-capped with short hydrophobic poly(methyl methacrylate) (PMMA) blocks in dilute aqueous solution and thin films. The self-assembly behavior depends on the degrees of ionization α of the P2VP and PDMAEMA blocks, which are altered in a wide range by varying the pH value. High degrees of ionization of both blocks prevent structure formation, whereas microphase-separated nanostructures form for a partially charged and uncharged state. While in solutions, the nanostructure formation is governed by the dependence of the P2VP block solubility of the and the flexibility of the PDMAEMA blocks on α, in thin films, the dependence of the segregation strength on α is key. Furthermore, the solution state plays a crucial role in the film formation during spin-coating. Overall, both the mixing behavior of the 3 types of blocks and the block sequence, governing the bridging behavior, result in strong variations of the nanostructures and their repeat distances.
AB - Multiblock copolymers with charged blocks are complex systems that show great potential for enhancing the structural control of block copolymers. A pentablock terpolymer PMMA-b-PDMAEMA-b-P2VP-b-PDMAEMA-b-PMMA is investigated. It contains two types of midblocks, which are weak cationic polyelectrolytes, namely poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-vinylpyridine) (P2VP). Furthermore, these are end-capped with short hydrophobic poly(methyl methacrylate) (PMMA) blocks in dilute aqueous solution and thin films. The self-assembly behavior depends on the degrees of ionization α of the P2VP and PDMAEMA blocks, which are altered in a wide range by varying the pH value. High degrees of ionization of both blocks prevent structure formation, whereas microphase-separated nanostructures form for a partially charged and uncharged state. While in solutions, the nanostructure formation is governed by the dependence of the P2VP block solubility of the and the flexibility of the PDMAEMA blocks on α, in thin films, the dependence of the segregation strength on α is key. Furthermore, the solution state plays a crucial role in the film formation during spin-coating. Overall, both the mixing behavior of the 3 types of blocks and the block sequence, governing the bridging behavior, result in strong variations of the nanostructures and their repeat distances.
KW - block polymers
KW - dynamic light scattering
KW - grazing-incidence small-angle X-ray scattering
KW - pH-responsive polymers
KW - self-assembly
KW - small-angle X-ray scattering
KW - thin films
UR - http://www.scopus.com/inward/record.url?scp=85107130737&partnerID=8YFLogxK
U2 - 10.1002/adfm.202102905
DO - 10.1002/adfm.202102905
M3 - Article
AN - SCOPUS:85107130737
SN - 1616-301X
VL - 31
JO - Advanced Functional Materials
JF - Advanced Functional Materials
IS - 32
M1 - 2102905
ER -