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Crystalline Carbosilane-Based Block Copolymers: Synthesis by Anionic Polymerization and Morphology Evaluation in the Bulk State
2022, Hübner, Hanna, Niebuur, Bart‐Jan, Janka, Oliver, Gemmer, Lea, Koch, Marcus, Kraus, Tobias, Kickelbick, Guido, Stühn, Bernd, Gallei, Markus
Block copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains.
A block copolymer templated approach for the preparation of nanoporous polymer structures and cellulose fiber hybrids by ozone treatment
2022, Gemmer, Lea, Hu, Qiwei, Niebuur, Bart-Jan, Kraus, Tobias, Balzer, Bizan N., Gallei, Markus
Functional amphiphilic block copolymers (BCPs) are versatile, smart, and promising materials that are often used as soft templates in nanoscience. BCPs generally feature the capability of microphase-separation leading to various interesting morphologies at the nanometer length scale. Materials derived from BCPs can be converted into porous structures while retaining the underlying morphology of the matrix material. Here, a convenient and scalable approach for the fabrication of porous functional polyvinylpyridines (P2VP) is introduced. The BCP polyisoprene-block-P2VP (PI-b-P2VP) is obtained via sequential anionic polymerization of the respective monomers and used to form either BCP films in the bulk state or a soft template in a composite with cellulose fibers. Cross-linking of the BCPs with 1,4-diiodobutane is conducted and subsequently PI domains are selectively degraded inside the materials using ozone, while preserving the porous and tailor-made P2VP nanostructure. Insights into the feasibility of the herein presented strategy is supported by various polymer characterization methods comprising nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). The resulting bulk- and composite materials are investigated regarding their morphology and pore formation by scanning electron microscopy (SEM), atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). Furthermore, chemical conversions were examined by energy dispersive X-ray spectroscopy (EDS), attenuated total reflection Fourier-transformation infrared spectroscopy (ATR-FTIR) and water contact angle (WCA) measurements. By this convenient strategy the fabrication of functional porous P2VP in the bulk state and also within sustainable cellulose composite materials is shown, paving the synthetic strategy for the generation of a new family of stimuli-responsive sustainable materials.
Thermo-Responsive Ultrafiltration Block Copolymer Membranes Based on Polystyrene-block-poly(diethyl acrylamide)
2023, Frieß, Florian V., Hartmann, Frank, Gemmer, Lea, Pieschel, Jens, Niebuur, Bart‐Jan, Faust, Matthias, Kraus, Tobias, Presser, Volker, Gallei, Markus
Within the present work, a thermo-responsive ultrafiltration membrane is manufactured based on a polystyrene-block-poly(diethyl acrylamide) block copolymer (BCP). The poly(diethyl acrylamide) block segment features a lower critical solution temperature (LCST) in water, similar to the well-known poly(N-isopropylacrylamide), but having increased biocompatibility and without exhibiting a hysteresis of the thermally induced switching behavior. The BCP is synthesized via sequential “living” anionic polymerization protocols and analyzed by 1H-NMR spectroscopy, size exclusion chromatography, and differential scanning calorimetry. The resulting morphology in the bulk state is investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) revealing the intended hexagonal cylindrical morphology. The BCPs form micelles in a binary mixture of tetrahydrofuran and dimethylformamide, where BCP composition and solvent affinities are discussed in light of the expected structure of these micelles and the resulting BCP membrane formation. The membranes are manufactured using the non-solvent induced phase separation (NIPS) process and are characterized via scanning electron microscopy (SEM) and water permeation measurements. The latter are carried out at room temperature and at 50 °C revealing up to a 23-fold increase of the permeance, when crossing the LCST of the poly(diethyl acrylamide) block segment in water.
Polyacrylonitrile-containing amphiphilic block copolymers: self-assembly and porous membrane formation
2023, Gemmer, Lea, Niebuur, Bart-Jan, Dietz, Christian, Rauber, Daniel, Plank, Martina, Frieß, Florian V., Presser, Volker, Stark, Robert W., Kraus, Tobias, Gallei, Markus
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).
Nanoporous Block Copolymer Membranes with Enhanced Solvent Resistance Via UV-Mediated Cross-Linking Strategies
2021, Frieß, Florian V., Hu, Qiwei, Mayer, Jannik, Gemmer, Lea, Presser, Volker, Balzer, Bizan N., Gallei, Markus
In this work, a block copolymer (BCP) consisting of poly((butyl methacrylate-co-benzophenone methacrylate-co-methyl methacrylate)-block-(2-hydroxyethyl methacrylate)) (P(BMA-co-BPMA-co-MMA)-b-P(HEMA)) is prepared by a two-step atom-transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self-assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4-dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV-mediated cross-linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross-linked and cross-linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross-linking on the porous structures. Finally, the influence of the herein described cross-linking protocols on water-flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV-mediated cross-linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies.