Nanoporous Block Copolymer Membranes with Enhanced Solvent Resistance Via UV-Mediated Cross-Linking Strategies.

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.

Ferrocene-Modified Polyacrylonitrile-Containing Block Copolymers as Preceramic Materials.

In the pursuit of fabricating functional ceramic nanostructures, the design of preceramic functional polymers has garnered significant interest. With their easily adaptable chemical composition, molecular structure, and processing versatility, these polymers hold immense potential in this field. Our study succeeded in focusing on synthesizing ferrocene-containing block copolymers (BCPs) based on polyacrylonitrile (PAN). The synthesis is accomplished via different poly(acrylonitrile-block-methacrylate)s via atom transfer radical polymerization (ATRP) and activators regenerated by electron transfer ATRP (ARGET ATRP) for the PAN macroinitiators. The molecular weights of the BCPs range from 44 to 82 kDa with dispersities between 1.19 and 1.5 as determined by SEC measurements. The volume fraction of the PMMA block ranges from 0.16 to 0.75 as determined by NMR. The post-modification of the BCPs using 3-ferrocenyl propylamine has led to the creation of redox-responsive preceramic polymers. The thermal stabilization of the polymer film has resulted in stabilized morphologies based on the oxidative PAN chemistry. The final pyrolysis of the sacrificial block segment and conversion of the metallopolymer has led to the formation of a porous carbon network with an iron oxide functionalized surface, investigated by scanning electron microscopy (SEM), energy dispersive X-ray mapping (EDX), and powder X-ray diffraction (PXRD). These findings could have significant implications in various applications, demonstrating the practical value of our research in convenient ceramic material design.