Search Results (7)

Fully room temperature three-dimensional (3D) shape-reprogrammable, recyclable, and photomobile azobenzene (azo) polymer actuators hold much promise in many photoactuating applications, but their development is challenging. Herein, we report on the efficient synthesis of a series of main-chain azo liquid crystalline polymers (LCPs) with such performances via Michael addition polymerization. They have both ester groups and two kinds of hydrogen bond-forming groups (i.e., amide and secondary amino groups) and different flexible spacer length in the backbones. Such poly(ester-amide-secondary amine)s (PEAsAs) show low glass transition temperatures (T_g ≤ 18.4 °C), highly ordered smectic liquid crystalline phases, and reversible photoresponsivity. Their uniaxially oriented fibers fabricated via the melt spinning method exhibit good mechanical strength and photoinduced reversible bending/unbending and large stress at room temperature, which are largely influenced by the flexible spacer length of the polymers. Importantly, all these fibers can be easily reprogrammed under strain at 25 °C into stable fiber springs capable of showing a totally different photomobile mode (i.e., unwinding/winding), mainly owing to the presence of low T_g and both dynamic hydrogen bonding and stable crystalline domains (induced by the uniaxial drawing during the fiber formation). They can also be recycled from a solution at 25 °C. This work not only presents the first azo LCPs with 3D shape reprogrammability, recyclability, and photomobility at room temperature, but also provides some important knowledge of their structure–property relationship, which is useful for designing more advanced photodeformable azo polymers. Full article

Stable, cross-linked, liquid crystalline polymer (LCP) films for membrane separation applications have been fabricated from the mesogenic monomer 11-(4-cyanobiphenyl-4′-yloxy) undecyl methacrylate (CNBPh), non-mesogenic monomer 2-ethylhexyl acrylate (2-EHA), and cross-linker ethylene glycol dimethacrylate (EGDMA) using an in-situ free radical polymerization technique with UV initiation. The phase behavior of the LCP membranes was characterized using differential scanning calorimetry (DSC) and X-ray scattering, and indicated the formation of a nematic liquid crystalline (LC) phase above the glass transition temperature. The single gas transport behavior of CO₂, CH₄, propane, and propylene in the cross-linked LCP membranes was investigated for a range of temperatures in the LC mesophase and the isotropic phase. Solubility of the gases was dependent not only on the condensability in the LC mesophase, but also on favorable molecular interactions of penetrant gas molecules exhibiting a charge separation, such as CO₂ and propylene, with the ordered polar mesogenic side chains of the LCP. Selectivities for various gas pairs generally decreased with increasing temperature and were discontinuous across the nematic–sotropic transition. Sorption behavior of CO₂ and propylene exhibited a significant change due to a decrease in favorable intermolecular interactions in the disordered isotropic phase. Higher cross-link densities in the membrane generally led to decreased selectivity at low temperatures when the main chain motion was limited by the lack of mesogen mobility in the ordered nematic phase. However, at higher temperatures, increasing the cross-link density increased selectivity as the cross-links acted to limit chain mobility. Mixed gas permeation measurements for propylene and propane showed close agreement with the results of the single gas permeation experiments. Full article

Two series of thermotropic liquid-crystalline polymers (TLCPs) were synthesized by reacting various dialkoxy terephthalate units with hydroquinone (HQ) and 2,6-naphthalene diol (Naph). The dialkoxy terephthalate moieties used in this study include 2,5-diethoxyterephthalate, 2,5-dibutoxyterephthalate, and 2,5-dihexyloxy-terephthalate. All the TLCPs synthesized in this study formed nematic phases. The molecular motions according to the length of the dialkoxy side groups in the TLCPs were evaluated by ¹³C cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy. The thermal properties and molecular dynamics of the TLCPs are found to be affected by the length of the dialkoxy side group and the aromatic diol unit in the main chain. Further, the thermal behaviors, liquid crystalline mesophases, and degree of crystallinity of the two series of TLCPs, i.e., HQ- and Naph-TLCPs, are compared. Full article

While only a few studies have investigated the synthesis of main chain-type polyazobenzenes, they continue to draw an increasing amount of attention owing to their industrial applications in holography, dyes, and functional adhesives. In this study, dibromoazobenzene was prepared as a monomer for constructing azo-based π-conjugated polymers. Miyaura–Suzuki cross-coupling polymerization was conducted to develop copolymers containing an azobenzene unit as a photoisomerization block and a pyrimidine-based liquid crystal generator block. The prepared polymers exhibited thermotropic liquid crystallinity and underwent cis and trans photoisomerization upon irradiation with ultraviolet and visible light. Furthermore, the photoisomerization behavior was examined using optical absorption spectroscopy and synchrotron X-ray diffraction spectrometry. Full article

Conventional shape memory polymers suffer the drawbacks of low thermal stability, low strength, and low shape recovery speed. In this study, main-chain liquid crystalline polyurethane (LCPU) that contains polar groups was synthesized. Graphene oxide (GO)/LCPU composite was fabricated using the solution casting method. The tensile strength of GO/LCPU was 1.78 times that of neat LCPU. In addition, shape recovery speed was extensively improved. The average recovery rate of sample with 20 wt % GO loading was 9.2°/s, much faster than that of LCPU of 2.6°/s. The enhancement in mechanical property and shape memory behavior could be attributed to the structure of LCPU and GO, which enhanced the interfacial interactions between GO and LCPU. Full article

Because of their extraordinary properties, such as high thermal stability, flame retardant, high chemical resistance and high mechanical strength, thermotropic liquid crystalline polymers (TLCPs) have recently gained more attention while being useful for many applications which require chemical inertness and high strength. Due to the recent advance in nanotechnology, TLCPs are usually compounded with nanoparticles to form particulate composites to enhance their properties, such as barrier properties, electrical properties, mechanical properties and thermal properties. Carbon-based nanofillers such as carbon nanotube (CNT), graphene and graphene oxide are the most common fillers used for the TLCP matrices. In this review, we focus on recent advances in thermotropic main-chain liquid crystalline polymer nanocomposites incorporated with CNTs. However, the biggest challenges in the preparation of CNT/TLCP nanocomposites have been shown to be inherent in the dispersion of CNTs into the TLCP matrix, the alignment and control of CNTs in the TLCP matrix and the load-transfer between the TLCP matrix and CNTs. As a result, this paper reviews recent advances in CNT/TLCP nanocomposites through enhanced dispersion of CNTs in TLCPs as well as their improved interfacial adhesion with the TLCP matrices. Case studies on the important role of chemically modified CNTs in the TLCP/thermoplastic polymer blends are also included. Full article

Phenylene-thiophene-based liquid crystalline π-conjugated copolymers bearing mesogenic groups as side chains were synthesized via a Stille polycondensation reaction and confirmed to exhibit a nematic liquid crystal phase at appropriate temperatures. The formation of a nematic phase, but not a smectic phase indicates cooperation of the main chain and side chain in the formation of a nematic main-chain/side-chain liquid crystal phase. The generation of polarons in the main chain as charge carriers during in-situ vapor doping of iodine is confirmed to increase with a doping progresses, exhibiting Dysonian paramagnetic behavior typical of conductive polymers. Full article