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Highly permeable organic solvent nanofiltration (OSN) membranes are desired to be used in an efficient and energy-saving chemical separation process. Herein, we fabricated a high-flux OSN membrane by synthesizing 7,7′-dihydroxy-2,2′-binaphthol (7,7′-OH-BINOL) as an aqueous phase monomer to react with trimesoyl chloride (TMC) via interfacial polymerization. The unique structures of 7,7′-OH-BINOL having a rotatable highly kinked unit and a rigid binaphthol ring endow the fabricated polyarylate membrane with very high microporosity and super-high Young's modulus. Both simulated and experimental results demonstrate that the BINOL-based polyarylate (PAR-BINOL) membrane has two types of micropores including cross-linked pores and stacked pores. Our results find that the PAR-BINOL membrane exhibits very high solvent permeance over a wide range of solvents with diverse polarity, and also possesses a long-term stable separation performance in solvents. Impressively, the membrane solvent permeance can reach up to 28.7 L m−2 h−1 bar−1, 9.2 L m−2 h−1 bar−1 and 6.7 L m−2 h−1 bar−1 for acetone, methanol, and dimethylformamide (DMF), respectively. The rejection of tetracycline (TC, Mw = 444 g mol−1) is 98.2%. Our work provides some insights into the molecular engineering of monomers with unique contorted and rigid structures for the fabrication of highly permeable OSN membranes.

It is known that the polyamide (PA) barrier layer's inherent microstructure and surface physicochemical properties of thin film composite nanofiltration membrane are crucial for its separation performance. Herein, we designed and synthesized a new zwitterionic aromatic diamine monomer 3-(4-(2-((4-aminophenyl)amino)ethyl)morpholino-4-ium)propane-1-sulfonate (PPD-MEPS) through a three steps reaction, and this hydrophilic molecule was incorporated into the active layer to tailor the poly(piperazine-amide)-based nanofiltration membranes with significantly improved water permeability and antifouling properties. As a p-phenylenediamine (PPD) derivative, PPD-MEPS possesses two active amine units, which can react with trimesoyl chloride in the organic phase during the interfacial polymerization reaction process. Thus, the super-hydrophilic zwitterions were not only on the membrane surface but also across the whole PA layer to facilitate water molecule transportation. The successful augmentation of zwitterions into the PA layer was well illustrated by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) results and X-ray photoelectron spectroscopy analysis. With increasing loading content of PPD-MEPS in PIP aqueous solution, the as-fabricated nanofiltration membranes (NFMs) exhibited higher hydrophilicity, increased active layer thickness, and molecular weight cut off. When the zwitterionic monomer reached 60% to PIP for NFM-4, the water permeability went up to 9.82 L m-2 h-1 bar-1, increasing by 45%; meanwhile, the Na2SO4/NaCl selectivity increased from 2.54 to 4.03. In addition, the fouling experiments illustrated that the fouling resistance of the zwitterion-modified NFMs to bovine serum albumin was significantly improved.

As known, piperazine (PIP) and m-phenylenediamine (MPD) are popularly employed as aqueous monomer to interfacially polymerize with trimesoyl chloride (TMC) for the fabrication of TFC polyamide NF and RO membrane, respectively. In this work, we designed a novel amine monomer 4-(piperazin-1-yl)benzene-1,3-diamine (PMPD) having the combined PIP and MPD units in one molecule and employing it with TMC to prepare the pristine nanofiltration membrane. Subsequently, zwitterionic antifouling PA surface was constructed by modification with 3-bromopropionic acid (3-BPA). The resulting membrane (PMPD-PA) exhibited a smoother surface with enhanced surface hydrophilicity than the membrane made from MPD, and the thickness of the PA active layer was down to ~35 nm. Meanwhile, its pure water permeability was ~19 L m−2 h−1 bar−1, with Na2SO4 rejection of 98.4%, and NaCl rejection as low as 24.1%, performing as a novel selective NF membrane. Furthermore, fouling tests using model foulants BSA and SA well illustrated the good antifouling properties of membrane PMPD-PA with the mitigated flux decline and enhanced flux recovery upon physical cleaning. Thus, this work further demonstrates the fabrication of high-performance TFC NF membrane from the perspective of molecular design.

Two novel OH-functionalized intrinsically microporous polymers were successfully synthesized from a tert-butyldimethylsilyl (TBS) protected 1,1′-binaphthalene-diamine monomer (NH2-BINOL-TBS). Interestingly, the polymerization and the removal of the TBS to form OH group happened at the same time. Polymers with 30% (PIM-HNTB-30) and 60% (PIM-HNTB-60) OH concentration were obtained by controlling the reaction time of 3.5 and 12 h, and confirmed by nuclear magnetic resonance spectroscopy (NMR). PIM-HNTB-30 exhibited higher Brunauer-Emmett-Teller (BET) surface area (432 vs 153 m2 g-1) and thermal stabilities (420 vs 385 °C) than PIM-HNTB-60. Both membranes showed modest gas permeabilities and selectivities, and PIM-HNTB-60 exhibited a relatively higher performance. After long-term aging or thermally annealed above glass transition temperature (Tg), both polymers exhibited a decreased permeabilities combined with a selectivity increase, and the 350 °C treated PIM-HNTB-60 exhibited O2 permeability of 89 Barrer and O2/N2 selectivity of 4.47. In all, the OH functionalization provided a good way to enhance the gas separation performance.

It is well known that the water flux and antifouling performance of polyamide (PA) membrane are strongly associated with their surface characters, especially for surface hydrophilicity, roughness, and charge. In this study, a zwitterionic surface TFC reverse osmosis (RO) membrane was fabricated by small molecule 3-bromopropionic (3-BPA) modification on the pristine membrane that fabricated through interfacial polymerization (IP) technique using a new aqueous monomer 4-morpholinobenzene-1,3-diamine (MpMPD) and trimesoyl chloride (TMC). The as-fabricated RO membranes were well analyzed by various techniques, that the zwitterionic MpMPD-PA membrane surface exhibited greatly enhanced hydrophilicity with water contact angle of 28.1° and surface roughness as low as 26.0 nm. The water permeability of membrane MpMPD-PA reached 1.65 L m−2 h−1 bar−1, which exhibited ~24% increase compared to our lab-made MPD membrane, meanwhile kept a high NaCl rejection of 97.8%. In addition, the dynamic fouling experiments illustrated that the zwitterionic surface RO membrane possess excellent fouling resistance to protein BSA, polysaccharides SA, and surfactant SDS. Therefore, this work provide a simple and convenient way to fabricate novel zwitterionic surface RO membrane with high performance from the molecular level design.

Electron-rich dioxynaphthalene (DNP) group bridged bifunctional ureidopyrimidinone (UPy) derivatives (L1, L2, and L3) were synthesized, which could form small cyclic monomers, oligomers, or linear supramolecular polymers at certain concentration in solution, to achieve a highly controllable ring–chain equilibrium self-assembling supramolecular system. The ring–chain equilibrium of these supramolecular monomers constructed by different lengths of oligo(ethylene oxide) (oligoEO) chain as spacers were investigated by a combination of techniques, such as 1H NMR, DOSY, single-crystal X-ray diffraction, and viscometry. The experiment results demonstrated that there exists intramolecular π–π stacking interaction between DNP group and intramolecularly dimerized UPy motif in the monomeric cyclic form of these supramolecular monomers, and the strength of this π–π stacking interaction directly depends on the length of the oligoEO chain. Furthermore, strong intramolecular π–π stacking interaction was found to promote...

A novel, bifunctional, quadruple hydrogen-bonding ureido-pyrimidinone (UPy) unit bridged by photochromic dithienylethene (1) has been synthesized, which affords linear assemblies in solution and undergoes concentration-dependent ring-opening polymerization. The two UPy functional groups of 1 can dimerize intramolecularly to form a cyclic monomer with the two thienyl rings fixed in a parallel conformation, which prohibits its photocyclization. We exploited the photochemical reactivity and resonance difference of the linker of the bis-UPy derivative as well as using the more typical (1)H NMR, DOSY, and Ubbelohde viscometry methods to investigate for the first time the ring-chain polymerization mechanism. Moreover, we fabricated a mixed polymer film with a fluorescent dye noncovalently endcapping the linear photochromic assemblies through quadruple hydrogen bonds, which showed nondestructive fluorescent read-out ability for data storage by fluorescence resonance energy transfer (FRET) from the fluorescent dye to the closed form of the diarylethene.

Large aggregates, constructed by linking together monomer building blocks via non-covalent interactions with polymer properties, are regarded as supramolecular polymers. Many kinds of non-covalent interactions, such as metal–ligand coordination, hydrogen bonding, π–π stacking, ionic interaction, and host–guest interaction etc., can be involved in the binding interactions of monomer building blocks, as well as in the modification of the side chain for the construction of variable supramolecular polymers. In this tutorial review, we summarized the reported supramolecular polymers fully- or partially-created from the combination of multiple non-covalent binding interactions, mainly of two kinds, in the orthogonal way.

Large aggregates, constructed by linking together monomer building blocks via non-covalent interactions with polymer properties, are regarded as supramolecular polymers. Many kinds of non-covalent interactions, such as metal–ligand coordination, hydrogen bonding, π–π stacking, ionic interaction, and host–guest interaction etc., can be involved in the binding interactions of monomer building blocks, as well as in the modification of the side chain for the construction of variable supramolecular polymers. In this tutorial review, we summarized the reported supramolecular polymers fully- or partially-created from the combination of multiple non-covalent binding interactions, mainly of two kinds, in the orthogonal way.

Novel linear supramolecular polymers, based on the combination of two classical binding interactions: the quadruple hydrogen bonding ureidopyrimidinone units and crown ether–paraquat host–guest recognition motifs, have been constructed from two heteroditopic monomers.