The liquid-crystalline (LC) phase structures and transitions of a combined main-chain/side-chain LC polymer (MCSCLCP) 1 obtained from radical polymerization of a 2-vinylterephthalate, poly(2,5-bis{[6-(4-butoxy-4'-oxybiphenyl) hexyl]oxycarbonyl}styrene), were studied using differential scanning calorimetry, one- and two-dimensional wide-angle X-ray diffraction (1D and 2D WAXD), and polarized light microscopy. We have found that 1 with sufficiently high molecular weight can self-assemble into a hierarchical structure with double orderings on the nanometer and subnanometer scales at low temperatures. The main chains of 1, which are rodlike as a result of the "jacketing" effect generated by the central rigid portion of the side chains laterally attached to every second carbon atom along the polyethylene backbone, form a 2D centered rectangular scaffold. The biphenyl-containing side chains fill the space between the main chains, forming a smectic E (SmE)-like structure with the side-chain axis perpendicular to that of the main chain. This biaxial orientation of 1 was confirmed by our 2D WAXD experiments through three orthogonal directions. The main-chain scaffold remains when the SmE-like packing is melted at elevated temperatures. Further heating leads to a normal smectic A (SmA) structure followed by the isotropic state. We found that when an external electric field was applied, the main-chain scaffold greatly inhibited the motion of the biphenyls. While the main chains gain a sufficiently high mobility in the SmA phase, macroscopic orientation of 1 can be achieved using a rather weak electric field, implying that the main and side chains with orthogonal directions can move cooperatively. Our work demonstrates that when two separate components, one offering the "jacketing" effect to the normally flexible backbone and the other with mesogens that form surrounding LC phases, are introduced simultaneously into the side chains, the polymer obtained can be described as an MCSCLCP with a fascinating hierarchically ordered structure.
Surface charge properties have a significant influence on membrane retention and fouling performance. As a key parameter describing the surface charge of membranes used in aqueous applications, zeta potential measurements on membranes of various types have attracted great attention. During the zeta potential characterization of a series of ion-conductive sulfonated poly(sulfone) membranes, it was found that the measured streaming current varied with the thickness of the sample, which is not predicted by the classical Smoluchowski equation. Moreover, for higher conductivity membranes with an increased concentration of sulfonate groups, the zeta potential tended toward zero. It was determined that the influence of membrane bulk conductance on the measured streaming current must be taken into account in order to correctly interpret the streaming current data for ion-conductive polymers and understand the relationship between membrane chemical composition and zeta potential. Extrapolating the measured streaming current to a membrane thickness of zero has proven to be a feasible method of eliminating the error associated with measuring the zeta potential on ion conductive polymer membranes. A linear resistance model is proposed to account for the observed streaming currents where the electrolyte channel is in parallel with the ion-conductive membranes.
Liquid crystalline elastomers (LCEs) using multivalent hydrogen bonds as cross-linkers were successfully fabricated, which showed both self-healing and photoinduced-deformable properties. More interestingly, this LCE could be readily molded into different shapes through a versatile and efficient procedure, and the fibrous and filmy samples showed different photoinduced-deformable behavior originating from the difference in molecular orientations.
Circularly polarized luminescent materials play an increasingly important role in display equipment and optical apparatuses. Herein, we design and synthesize a kind of luminescent liquid crystalline polymer with both chirality and aggregation-induced emission groups, namely, poly(4-cholesterol formate-oxygen-tetraphenylethylene-methacrylate) (PT-Chol). Polarized light microscopy and X-ray scattering results show that the polymer forms a layered structure. Because of the existence of the tetraphenylethylene luminogen, the polymer shows highly efficient circularly polarized luminescence (CPL) properties with a luminescence dissymmetry factor (g lum) of ∼+0.45 after blending a specified amount of 4-cyano-4′-pentyl biphenyl (5CB), although the pure polymer does not show any CPL behavior in the solid state. A further experimental result shows that the mixture of PT-Chol and 5CB can form a chiral nematic liquid crystal (N*-LC) or smectic C* (Sm C*) phase in low concentration, but the complete dissolution of PT-Chol in 5CB does not result in the development of CPL properties. Gradually increasing the concentration of PT-Chol leads to the development of aggregation-enhanced emission behavior in the 5CB solution, which results in highly efficient CPL properties in the Sm C* phase. At the same time, the obtained circularly polarized luminescent material shows excellent stability, which is conducive to its applications in optoelectronic devices.
A series of high efficiency luminescent liquid crystalline polymers (LLCPs) based on aggregation-induced emission (AIE) and the "Jacketing" effect, namely, poly{2,5-bis{[2-(4-oxytetraphenylethylene)-n-alkyl]oxycarbonyl}styrene} (denoted as Pm, m = 2, 4, 6, 8, 10, 12), were successfully designed and synthesized via introducing tetraphenylethylene to the side group with different length spacers. Because of the AIE effect, the resultant LLCPs are completely free of aggregation caused quenching. The photophysical properties and phase behavior were studied via various techniques such as UV−vis absorption spectra, photoluminescence spectra (PL), polarized light microscopy (PLM), differential scanning calorimetry (DSC), and variable temperature one-dimensional wide-angle X-ray diffraction (1D WAXD). The results revealed that the resultant monomers showed typical AIE behavior and the polymers exhibited aggregation enhanced emission (AEE) behavior. Moreover, due to the "Jacketing" effect, the polymers showed high efficiency luminescence in the liquid crystalline state, which was significantly dependent on the spacer length (the solid-state quantum yields decreased from 52% to 18% with increasing spacer length). Meanwhile, the glass transition temperatures (T g ) decreased with increasing the length of spacers. With increasing the spacer length, the phase structure transformed from smectic A (SmA) (Pms, m = 2, 4, 6) to hexagonal columnar phase (Col H ) (Pms, m = 8, 10, 12). All the polymers presented good filmforming property and processing performance, which made them be promising materials for the luminescent devices.
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