Martin-Luther-Universität Halle-Wittenberg

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Forschung

Nanostructured materialsNanopatterning
Block copolymers
Supramolecular polymers
Nanoparticles
Charge-storage materials
CapsulesNanoporosity
Catalysis
Biomaterials
Biomembranes
Polymer synthesisLiving radical polymerization (ATRP, NMP, RAFT)
Living cationic polymerization
ROMP
Polycondensation methods
Resin Materials
Polymeric materialsNanocomposites/Nanofillers
Resin materials
Self healing materials
Polymer technology
Polymer analyticsNMR-Analysis (1D-, 2D)
Mass spectrometry (MALDI, ESI-TOF)
Hyphenated Techniques (SEC-MALDI, ESI-TOF)
Chromatography (LC, SEC)
Surface analysis

Research - overview

Research activities are centered around the preparation of functional polymers (living polymerization methods, functionalization strategies, catalysis) and the transfer of the generated molecules into areas of biomimetic polymers (artificial membranes and molecular biomimicry), self-healing polymers and nanocomposites (self-healing in industrial polymeric materials, fuel cell membranes), nanostructured materials and polymeric liquids.

Biomimetic Polymers

Biomimetic Polymers

Research Area I: Polymer Synthesis / Catalysis

Polymer technology still is dominated by functional polymers, in turn enabling to control their threedimensional ordering and organization. Key-point in this endeavor is the synthetic control over architectural design, achieving synthetic and dimensional flexibility of macromolecules as well as a profound structural analysis. We do address these issues by methodological development of synthetic methods based on combinations of living polymerization techniques with reliable functionalization strategies known from synthetic organic chemistry, including "click"-based methods. Besides living radical polymerization techniques (ATPR, RAFT, NMP) a focus is placed on ROMP, GRIM and living cationic polymerization techniques (LCCP). Based on such approaches, polymer architectures (eg.: synthesis of functional graft-, cyclic-, star-polymers) as well as issues of site-specific integration of interactions (such as hydrogen bonds, ionomers, blockcopolymers) into tailored macromolecules can be enabled. Altogether this allows developments of a platform for the design of functional polymers, planning and directing various self-assembly processes.

Another important aspect concerns a true and reliable characterization of functionalized macromolecules in the sense of organic molecules, based on chromatographic techniques coupled to high resolution mass spectrometry. Besides the development of LC/ESI-MS and GPC/LC-MALDI-methods our main developments in this area are coupling interfaces to either ESI-TOF or MALDI-TOF-MS for the analysis of macromolecules or crossover-reactions. Thus a special feature concerns separation techniques of two-dimensional chromatography (2D-LC/GPC), which enables endgroup/block-specific separation and size-dependent identification of macromolecules using hyphenated direct MS-specific detection. This in turn enables to address the synthetic preparation of more complex polymeric architectures, in particular sequence-specific polymers and cyclic polymers in higher structural precision.

Selected references/research area I

Functional polymers by modification

(a) Binder, W. H.; Herbst, F., Click chemistry in polymer science. In McGraw-Hill Yearbook of Science & Technology, Blumel, D., Ed. McGraw-Hill: New York, 2011; pp 46-49 (review); (b) Binder, W. H.; Sachenshofer, R., "Click"-chemistry on supramolecular materials. In Click Chemistry for Biotechnology and Materials Science, Lahann, J., Ed. Wiley-Blackwell: 2009; pp 119-175 (review); (c) Binder, W. H.; Sachsenhofer, R., "Click" Chemistry in Polymer and Materials Science. Macromol. Rapid Commun. 2007, 28 (1), 15-54 (review); (d) Schulz, M.; Tanner, S.; Barqawi, H.; Binder*, W. H., Macrocyclization of polymers via ring-closing metathesis and azide/alkyne-"click"-reactions: An approach to cyclic polyisobutylenes. J. Polym. Sci., Part A: Polym. Chem. 2010, 48 (3), 671-680.

Living Polymerization

(a) Chen, S.; Ströhl, D.; Binder, W. H. Orthogonal Modification of Polymers via Thio–Bromo “Click” Reaction and Supramolecular Chemistry: An Easy Method Toward Head-to-Tail Self-Assembled Supramolecular Polymers. ACS Macro Letters 2015, 4, 48-52. (b) Chen, S.; Binder, W. H. Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization. Polymer Chemistry 2015, 6, 448-458. (c) Chen, S.; Deng, Y.; Chang, X.; Barqawi, H.; Schulz, M.; Binder, W. H. Facile preparation of supramolecular (ABAC)n multiblock copolymers from Hamilton wedge and barbiturate-functionalized RAFT agents. Polymer Chemistry 2014, 5, 2891-2900. (d) Enders, C.; Tanner, S.; Binder, W. H., End-Group Telechelic Oligo- and Polythiophenes by “Click” Reactions: Synthesis and Analysis via LC-ESI-TOF MS. Macromolecules 2010, 43 (20), 8436-8446. (e) Binder, W. H.; Gloger, D.; Weinstabl, H.; Allmaier, G.; Pittenauer, E., Telechelic Poly(N-isopropylacrylamides) via Nitroxide-Mediated Controlled Polymerization and "Click" Chemistry: Livingness and "Grafting-from" Methodology. Macromolecules 2007, 40 (9), 3097-3107. (f) Hackethal, K.; Döhler, D.; Tanner, S.; Binder, W. H., Introducing Polar Monomers into Polyisobutylene by Living Cationic Polymerization: Structural and Kinetic Effects Macromolecules 2010, 1761-1770; (g) Binder, W. H.; Kluger, C.: Combining Ring-Opening Metathesis Polymerization (ROMP) with Sharpless-Type "Click" Reactions: An Easy Method for the Preparation of Side Chain Functionalized Poly(oxynorbornenes). Macromolecules 2004, 37, 9321-9330.

Catalysis

(a) Shaygan Nia, A.; Rana, S.; Dohler, D.; Noirfalise, X.; Belfiore, A.; Binder, W. H. Click chemistry promoted by graphene supported copper nanomaterials. Chemical Communications 2014, 50, 15374-15377. (b) Döhler, D.; Michael, P.; Binder, W. H., Autocatalysis in the Room Temperature Copper(I)-Catalyzed Alkyne–Azide “Click” Cycloaddition of Multivalent Poly(acrylate)s and Poly(isobutylene)s. Macromolecules 2012, 45 (8), 3335-3345 (c) (c) Kurzhals, S.; Binder, W. H. Telechelic polynorbornenes with hydrogen bonding moieties by direct end capping of living chains. Journal of Polymer Science Part A: Polymer Chemistry 2010, 48, 5522-5532. (d) Binder, W. H.; Pulamagatta, B.; Kir, O.; Kurzhals, S.; Barqawi, H.; Tanner, S. Monitoring Block-Copolymer Crossover-Chemistry in ROMP: Catalyst Evaluation via Mass-Spectrometry (MALDI). Macromolecules 2009, 42, 9457-9466.

Analytics of polymers by development of hyphenated methods

(a) Barqawi, H.; Schulz, M.; Olubummo, A.; Sauerland, V.; Binder, W. H.: 2D-LC/SEC-(MALDI-TOF)-MS characterization of symmetric and nonsymmetric biocompatible PEOm-PIB-PEOn block copolymers. Macromolecules 2013, 46, 7638-7649 (b) Barqawi, H.; Ostas, E.; Liu, B.; Carpentier, J.-F.; Binder, W. H., Multidimensional Characterization of α,ω-Telechelic Poly(ε-caprolactone)s via Online Coupling of 2D Chromatographic Methods (LC/SEC) and ESI-TOF/MALDI-TOF-MS. Macromolecules 2012, 45, 9779–9790 (c) Kurzhals, S.; Enders, C.; Binder, W. H., Monitoring ROMP Crossover Chemistry via ESI-TOF MS. Macromolecules 2013, 46 (3), 597-607 (d) Enders, C.; Tanner, S.; Binder, W. H., End-Group Telechelic Oligo- and Polythiophenes by “Click” Reactions: Synthesis and Analysis via LC-ESI-TOF MS. Macromolecules 2010, 43 (20), 8436-8446.

Research Area II: Self healing polymers / Nanocomposites

Polymeric materials need new concepts to address new value-added markets. As often polymerization technology reaches constraints of improvement, new research areas can push the limit of exploitation into new markets. We do address new and emerging areas of polymer science, such as self-healing materials, fuel-cell membranes or issues of friction or wear, where control of the intrinsic three-dimensional structure of polymers is important for their improved function.  Thus, one current activity is dedicated to self-healing polymers - an immanent challenge in macromolecular chemistry, where a basic understanding of chemical and physical processes in polymers forms the basis for the design of new polymers with self-healing properties. Another field of research is dedicated to the molecular design of electrolyte membranes to enable improved design - a still challenging area in membrane-technology.  Furthermore, ionic and polymeric ionic liquids are enormously important components in membrane technology, sustainable chemistry as well as in the field of tribology. A development of these areas into the design of new electrolyte membranes, into the field of tribology and self-healing materials is envisioned.

Classical nanocomposite-materials based on silica and graphite can now be significantly improved by the use of carbon nanotubes or graphene, often hampered by their low dispersibility in polymeric matrices. Control of interfacial interaction between inorganic/organic nanocomposites has been addressed vastly in our group by using grafting-from technology and click-based surface modification of a large number of inorganic (nano/micro)-particles, thus effecting selective nanoparticle attachment or dispersion in poly(olefinic) matrices.

Selected references/research area II

Self healing polymers

(a) Self-Healing Polymers. From Principles to Applications.; Binder, W. H., Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2013, pp 425 pages (book). (b) Döhler, D.; Peterlik, H.; Binder, W. H. A dual crosslinked self-healing system: supramolecular and covalent network formation of four-arm star polymers. Polymer 2015, ASAP. (c) Philipp Michael, D. D., Wolfgang H. Binder. Improving Autonomous Self Healing via Combined Chemical / Physical Principles Polymer 2015, DOI:10.1016/j.polymer.2015.1001.1041    (review). (d) Guadagno, L.; Raimondo, M.; Naddeo, C.; Longo, P.; Mariconda, A.; Binder, W., H. Healing efficiency and dynamic mechanical properties of self-healing epoxy systems. Smart Mater. Struct. 2014, 23, 045001. (e) Akbarzadeh, J.; Puchegger, S.; Stojanovic, A.; Kirchner, H. O. K.; Binder, W. H.; Bernstorff, S.; Zioupos, P.; Peterlik, H. Timescales of self-healing in human bone tissue and polymeric ionic liquids. Bioinspired, Biomimetic and Nanobiomaterials 2014, 3, 123-130. (f) Herbst, F.; Seiffert, S.; Binder, W. H., Dynamic supramolecular poly(isobutylene)s as self-healing materials. Polymer Chemistry 2012, 3 (11), 3084-3092. (g) Herbst, F.; Döhler, D.; Michael, P.; Binder, W. H., Self-healing polymers via supramolecular forces. Macromol. Rapid Commun. 2013, 34 (3), 203-220 (review). (h) Gragert, M.; Schunack, M.; Binder, W. H., Azide/Alkyne-“Click”-Reactions of Encapsulated Reagents: Toward Self-Healing Materials. Macromol. Rapid Commun. 2011, 32 (5), 419-425.

Polymeric ionic liquids/tribology

(a) Stojanovic, A.; Appiah, C.; Dohler, D.; Akbarzadeh, J.; Zare, P.; Peterlik, H.; Binder, W. H.: Designing melt flow of poly(isobutylene)-based ionic liquids. Journal of Materials Chemistry A 2013, 1, 12159-12169 (c) Zare, P.; Mahrova, M.; Tojo, E.; Stojanovic, A.; Binder, W. H., Ethylene glycol-based ionic liquids via azide/alkyne click chemistry. J. Polym. Sci. Part A: Polymer Chemistry 2013, 1 (51), 190-202. (d) Pagano, F.; Gabler, C.; Zare, P.; Mahrova, M.; Dörr, N.; Bayon, R.; Fernandez, X.; Binder, W. H.; Hernaiz, M.; Tojo, E.; Igartua, A.: Dicationic ionic liquids as lubricants. Proc. I. Mech. Eng., Part J: J. Engineering Tribology 2012, 226, 952-964. (e) Swath, P., Chen, X., Sharma, V., Igartua, M. A., Pagano, F., Binder, W. H., Zare, P., Doerr, N., Synergistic mixtures of ionic liquids with other ionic liquids and/or with ashless thiophosphates for antiwear and/or friction reduction applications. WO 2013169779 (2013).

Fuel-cell membranes

(a) Li, N.; Guiver, M. D.; Binder, W. H.: Towards High Conductivity in Anion-Exchange Membranes for Alkaline Fuel Cells. ChemSusChem 2013, 6, 1376–1383. (b) Li, N.; Yan, T.; Li, Z.; Thurn-Albrecht, T.; Binder, W. H.: Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes. Energy & Environmental Science 2012, 5, 7888-7892.

Nanocomposites

Kir, O.; Binder, W. H.: Living anionic surface initiated polymerization (LASIP) of isoprene from silica nano- and glass particles. European Polymer Journal 2013, 49, 3078-3088; (b) Zirbs, R.; Binder, W. H.; Gahleitner, M.; Machl, D.: Impact modification of polyolefins Borealis Technology Oy, F., Ed., 2009; Vol. WO 2009016188; (c) Binder, W. H.; Zirbs, R.; Machl, D.; Gahleitner, M.: Grafting Polyisobutylene from Nanoparticle Surfaces: Concentration and Surface Effects on Livingness. Macromolecules 2009, 2, 7379-7387. (d) Li, N.; Binder, W. H.: Click-Chemistry for Nanoparticle-Modification. J. Mater. Chem. 2011, 21, 16717 - 16734 (review).

Research Area III: Biomimetic polymers

Application of polymers within living organisms requires concepts to implement biocompatibility and bioavailability, additionally introducing biomimicry via molecular design. We thus are expanding the interplay between polydisperse macromolecules and biological molecules by hybrid-materials displaying properties useful for living organisms. Polymers and lipid molecules meet in their dynamic and amphiphilic character when present at interfaces, specifically within artificial bilayer-membranes. Current activities aim at the engineering of monolayers and closed-bilayer capsules, generated from either lipid vesicles and/or polymersomes, addressing enhanced mechanical stability as well as  controlled porosity of the final capsules useful for drug delivery and artificial folding.

A particular emphasis is directed towards the understanding of lipid/polymer interaction in ordered assemblies at the bilayer-interface, allowing to assemble nanosized objects (nanoparticles, large (amphiphilic) biomolecules or biochemical receptors) at specific locations of an interface, either on a polymer/lipid (membrane)-interface, or at liquid/liquid interfaces. Main aims here concern the use of amphiphilic, biocompatible polymers for use in medicine and drug delivery, generating membranes with unusual properties based on the microphase separation of blockcopolymers. Together with introduced STEALTH-properties (via eg. PEG- or poly(oxazoline)s) these membranes are highly variable in their properties with respect to their selective permeability towards nanoparticles and small molecular aggregates, enabling issues of receptor clustering and triggering.

Selected references/research area III

Biomimetic Polymers

(a) Malke, M.; Barqawi, H.; Binder, W. H. Synthesis of an Amphiphilic β-Turn Mimetic Polymer Conjugate. ACS Macro Letters 2014, 3, 393-397. (b) M.; Olubummo, A.; Bacia, K.; Binder, W. H. Lateral surface engineering of hybrid lipid-BCP vesicles and selective nanoparticle embedding. Soft Matter 2014, 10, 831-839. (c) Schulz, M.; Werner, S.; Bacia, K.; Binder, W. H., Controlling Molecular Recognition with Lipid/Polymer Domains in Vesicle Membranes. Angew. Chem. Int. Ed. 2013, 52 (6), 1829-1833. (d) Binder, W. H., Polymer-Induced Transient Pores in Lipid Membranes. Angew. Chem. Int. Ed. 2008, 47 (17), 3092-3095; (e) Binder, W. H.; Barragan, V.; Menger, F. M., Domains and Rafts in Lipid Membranes. Angew. Chem., Int. Ed. 2003, 42 (47), 5802-5827 (review).

Interfacial effects and nanoparticle attachment

(a) Olubummo, A.; Schulz, M.; Lechner, B.-D.; Scholtysek, P.; Bacia, K.; Blume, A.; Kressler, J.; Binder, W. H., Controlling the Localization of Polymer-Functionalized Nanoparticles in Mixed Lipid/Polymer Membranes. ACS Nano 2012, 6 (10), 8713–8727. (b) Schulz, M.; Olubummo, A.; Binder, W. H., Beyond the Lipid-Bilayer: Interaction of Polymers and Nanoparticles with Membranes. Soft Matter 2012, 8 (18), 4849–4864 (review). (c) Binder, W. H., Supramolecular Assembly of Nanoparticles at Liquid-Liquid Interfaces. Angew. Chem., Int. Ed. 2005, 44 (33), 5172-5175. (d) Binder, W. H.; Sachsenhofer, R., Polymersome/Silica Capsules by "Click"-Chemistry. Macromol. Rapid Commun. 2008, 29 (12-13), 1097-1103. (e) Li, H.; Pfefferkorn, D.; Binder, W. H.; Kressler, J., Phospholipid Langmuir Film as Template for in Situ Silica Nanoparticle Formation at the Air/Water Interface. Langmuir 2009, 25 (23), 13328-13331.

Research Area IV: Nanoscopic ordering of nanoparticles onto functional macromolecules

Spatially separated domains in blockcopolymers can be used as scaffolds for assembly processes, in particular for the attachment of nanoparticles and nanosized objects. One main focus of activities is directed to the synthesis and use of designed polymeric surfaces and interfaces enabling the stable binding of nanoparticles onto derivatized (microphase-separated) surfaces for further use in solar-cell-technology, energy storage and catalysis. Self-assembly-processes of nanosized objects (i.e.: Au-NP’s, CdSeNP’s, CdSe-nanorods) on specific locations of the surface are studied, extending this concept to the assembly of BCP’s within nanotubes (50 - 400 nm, Al2O3) by melt- or solution infiltration of block-copolymers (BCPs), generating tubular structures with multi-walled architectures.

TEM-measurements of the generated BCP’s reveal complex tube-wall morphologies consisting of concentric lamellae parallel to the tube axis, thus enabling control over the chemical functionalities. The crystallization of polymer segments within the polymer chain can serve as additional structuring force for the self assembly into 2D- and 3D-array structures and is investigated as an additional driving force for patterning and structure formation. Photoactive materials for solar cell technology or catalysis by selectively embedded nanoparticles are two possible applications of these research investigations.

Selected references/research area IV

Nanostructured Materials

(a) Pulamagatta, B.; Yau, M. Y. E.; Gunkel, I.; Thurn-Albrecht, T.; Schröter, K.; Pfefferkorn, D.; Kressler, J.; Steinhart, M.; Binder, W. H., Block Copolymer Nanotubes by Melt-infiltration of Nanoporous Aluminum Oxide. Adv. Mater. 2011, 23 (6), 781-786. (b) Li, N.; Binder, W. H. Click-Chemistry for Nanoparticle-Modification. J. Mater. Chem. 2011, 21, 16717 - 16734. (c) Haryono, A.; Binder, W. H., Controlled Arrangement of Nanoparticle Arrays in Block-Copolymer Domains. Small 2006, 2 (5), 600-611. (d) Shaygan Nia, A.; Enders, C.; Binder, W. H., Hydrogen-Bonded Perylene/Terthiophene-Materials: Synthesis and Spectroscopic Properties. Tetrahedron 2012, 68 (2), 722-729. (e) Kir, O.; Hüsing, N.; Enke, D.; Binder, W. H., TEMPO Containing Polynorbornene Block Copolymers Prepared via ROMP and Their use as Scaffolds in Sol/Gel-Process. Macromol. Symp. 2010, 293 (1), 67-70. (f) Binder, W. H.; Sachsenhofer, R.; Straif, C. J.; Zirbs, R., Surface-modified nanoparticles via thermal and Cu(i)-mediated "click" chemistry: Generation of luminescent CdSe nanoparticles with polar ligands guiding supramolecular recognition. J. Mater. Chem. 2007, 17 (20), 2125-2132.

Polymeric Ionic Liquids/Nanostructured Interfaces

(a) Osim, W.; Stojanovic, A.; Akbarzadeh, J.; Peterlik, H.; Binder, W. H.: Surface modification of MoS2 nanoparticles with ionic liquid-ligands: towards highly dispersed nanoparticles. Chemical Communications 2013, 49, 9311-9313. (b) Ostas, E.; Yan, T.; Thurn-Albrecht, T.; Binder, W. H.* Crystallization of Supramolecular Pseudoblock Copolymers. Macromolecules 2013, 46, 4481-4490. (c) Zare, P.; Stojanovic, A.; Herbst, F.; Akbarzadeh, J.; Peterlik, H.; Binder, W. H. Hierarchically Nanostructured Polyisobutylene-Based Ionic Liquids. Macromolecules 2012, 45, 2074-2084.

Research activities / Industrial Research

Current projects include the synthesis and investigation of high performance resins and nanomaterials for chemical industry, based on research results gained from basic research. This includes industrial research projects on self-healing materials, nanocomposites and resin-materials.

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