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Phase Behavior of Melts of Diblock-Copolymers with One Charged Block
In this work, we investigated the phase behavior of melts of block-copolymers with one charged block by means of dissipative particle dynamics with explicit electrostatic interactions. We assumed that all the Flory–Huggins χ parameters were equal to 0. We showed that the charge- correlation attraction solely can cause microphase separation with a long-range order; a phase diagram was constructed by varying the volume fraction of the uncharged block and the electrostatic interaction parameter λ (dimensionless Bjerrum length). The obtained phase diagram was compared to the phase diagram of “equivalent” neutral diblock-copolymers with the non-zero χ-parameter between the beads of different blocks. The neutral copolymers were constructed by grafting the counterions to the corresponding co-ions of the charged block with further switching off the electrostatic interactions. Surprisingly, the differences between these phase diagrams are rather subtle; the same phases in the same order are observed, and the positions of the order-disorder transition ODT points are similar if the λ-parameter is considered as an “effective” χ-parameter. Next, we studied the position of the ODT for lamellar structure depending on the chain length N. It turned out that while for the uncharged diblock copolymer the product χcrN was almost independent of N, for the diblock copolymers with one charged block we observed a significant increase in λcrN upon increasing N. This can be attributed to the fact that the counterion entropy prevents the formation of ordered structures, and its influence is more pronounced for longer chains since they undergo the transition to ordered structures at smaller values of λ, when the electrostatic energy becomes comparable to kbT. This was supported by studying the ODT in diblock-copolymers with charged blocks and counterions cross-linked to the charged monomer units. The ODT for such systems was observed at significantly lower values of λ, with the difference being more pronounced at longer chain lengths N. The fact that the microphase separation is observed even at zero Flory–Huggins parameter can be used for the creation of “high-χ” copolymers: The incorporation of charged groups (for example, ionic liquids) can significantly increase the segregation strength. The diffusion of counterions in the obtained ordered structures was studied and compared to the case of a system with the same number of charged groups but a homogeneous structure; the diffusion coefficient along the lamellar plane was found to be higher than in any direction in the homogeneous structure.
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)-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).