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

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

Thermo-Responsive Ultrafiltration Block Copolymer Membranes Based on Polystyrene-block-poly(diethyl acrylamide)

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

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

Thermo-Responsive Ultrafiltration Block Copolymer Membranes Based on Polystyrene-block-poly(diethyl acrylamide)

Within the present work, a thermo-responsive ultrafiltration membrane ismanufactured based on a polystyrene-block-poly(diethyl acrylamide) blockcopolymer (BCP). The poly(diethyl acrylamide) block segment features a lowercritical solution temperature (LCST) in water, similar to the well-knownpoly(N-isopropylacrylamide), but having increased biocompatibility andwithout exhibiting a hysteresis of the thermally induced switching behavior.The BCP is synthesized via sequential “living” anionic polymerizationprotocols and analyzed by1H-NMR spectroscopy, size exclusionchromatography, and differential scanning calorimetry. The resultingmorphology in the bulk state is investigated by transmission electronmicroscopy (TEM) and small-angle X-ray scattering (SAXS) revealing theintended hexagonal cylindrical morphology. The BCPs form micelles in abinary mixture of tetrahydrofuran and dimethylformamide, where BCPcomposition and solvent affinities are discussed in light of the expectedstructure of these micelles and the resulting BCP membrane formation. Themembranes are manufactured using the non-solvent induced phaseseparation (NIPS) process and are characterized via scanning electronmicroscopy (SEM) and water permeation measurements. The latter arecarried out at room temperature and at 50°C revealing up to a 23-foldincrease of the permeance, when crossing the LCST of the poly(diethylacrylamide) block segment in water

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

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)-bpoly(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)