Crosslinked Liquid Crystal Polymer Research Articles

Photothermal‐Responsive Crosslinked Liquid Crystal Polymers

AbstractCrosslinked liquid crystal polymers (CLCPs) are a promising type of smart polymer material with excellent two‐way shape memory behavior under the stimulation of various external conditions. Among the various external stimuli, light with the advantages of instantaneity, high accuracy, remote controllability, pollution‐free, etc., has been widely used in the control of CLCPs. Traditional photoresponsive CLCP systems based on photoisomerization are limited by the penetration depth of ultraviolet light, the number of useful photochemical reactions, and long‐term stability. Recently, a strategy for designing photoresponsive CLCPs based on the photothermal effect has attracted scientific attention. Photothermal materials in the CLCP matrix can convert light into heat through plasma resonance or energy transition under the light irradiation of a certain wavelength, and locally heat the CLCP matrix to beyond the liquid crystal‐to‐isotropic phase transition temperature, thus achieving reversible macroscopic deformation. Combining photothermal materials and CLCPs can decrease the dependence on specific photosensitive groups such as azobenzene mesogens and endow photoresponsive CLCPs with design flexibility. Herein, the photothermal‐responsive CLCPs under the stimulations of different light wavelengths and their application fields are reviewed. In addition, the current challenges in the field of photothermal‐responsive CLCPs are summarized, and a brief outlook on future development is proposed.

Photoindeuced bending behavior of uniaxial aligned crosslinked NBA liquid crystalline polymer films

Crosslinked liquid crystal polymers (CLCPs) have recently attracted much attention because they exhibit unique properties in stimuli responsiveness. We have recently focused on the photoinduced deformation behavior of CLCP containing N-benzylideneaniline (NBA) as a photoresponsive moiety. We prepared two types uniaxially aligned NBA-containing crosslinked liquid crystalline polymer film, homogeneous and homeotropic, and evaluated its photomechanical properties. The initial alignment of photoactive mesogens significantly affects the bending behavior of the CLCP films: the homogeneous films bent toward the irradiation direction of the actinic UV light, while the homeotropic films bent away from the light source.

Broadband integrated optic polarization splitters by incorporating polarization mode extracting waveguide

A compact integrated optic polarization splitter is highly anticipated for polarization multiplexed optical communications, dual polarization optical sensors, single photon quantum signal processing, etc. In this work, we propose and demonstrate a polarization mode extracting device using a highly birefringent crosslinked liquid crystal polymer, reactive mesogen. The device includes the birefringent material inserted into a Y-branch optical waveguide to extract the TE polarized mode. A polarization splitting ratio of 27 dB was obtained, and a crosstalk of less than −25 dB was maintained for a wavelength range of 1500~1600 nm. The device exhibited good thermal stability at 100 °C for 12 hours. The broadband operating characteristic is a unique advantage of the proposed mode extracting polarization splitter.

Dual-responsive deformation of a crosslinked liquid crystal polymer film with complex molecular alignment.

Crosslinked liquid crystal polymers (CLCPs) containing azobenzene mesogens have been developed as stimuli-responsive materials, which can undergo photodeformation and thus convert light energy into mechanical force. The deformation behavior of CLCPs is strongly influenced by the alignment of the mesogens; however, a precise control of the alignment domain at micro-scale is still a challenge. Here we report complex molecular alignment in the CLCP film by using photoalignment technology. First, azo dye SD1 is aligned in-plane by UV light with a discrete alternating striped director profile. The SD1 molecules in adjacent strips are aligned orthogonal, and the widths of the strips are controlled in several hundred micrometers by a photomask with grating patterns. Then the liquid crystal molecules in the CLCP film are aligned by SD1 through the anchoring effect on one side (SD1 side), and aligned perpendicular by the polyimide (PI) alignment layer on the other side (PI side). With these alignments, two kinds of splayed structures are formed through the depth of the film. When irradiated by UV light, the film bends toward the SD1 side with the bending direction along the diagonal of the film, determined by the resultant direction of molecular alignment on the SD1 side. When irradiated by blue light and heat, the bending direction is along the edge of the film. This dual-responsive deformable film with complex alignment is anticipated to be used in shape-changing biomedical devices, multiple controllable switches, and microactuators.

Humidity‐ and Photo‐Induced Mechanical Actuation of Cross‐Linked Liquid Crystal Polymers

Azobenzene-containing cross-linked liquid crystal polymer films without hydrophilic groups exhibit dual-responsivity to humidity and UV light. The films realize not only a series of large and sophisticated contactless motions by utilizing moisture, including an inchworm walk, and tumbling locomotion, but also dual-mode actuation that can be applied in flexible electronics.

Visible Light Responsive Liquid Crystal Polymers Containing Reactive Moieties with Good Processability.

Two types of novel reactive linear liquid crystal polymers (LLCPs) with different azotolene concentrations have been synthesized and processed into films and fibers by solution and melting processing methods. Then, the LLCPs in the obtained monodomain fiber and polydomain film were easily cross-linked with difunctional primary amines. The resulted cross-linked liquid crystal polymers (CLCPs) underwent reversible photoinduced bending and unbending behaviors in response to 445 and 530 nm visible light at room temperature, respectively. The post-cross-linking method provides a facile way to prepare the CLCP films and fibers with different shapes from LLCPs, which can be processed by traditional melting and solution methods.

Deformation of cross-linked liquid crystal polymers by light – from ultraviolet to visible and infrared

ABSTRACTCollecting and amplifying the nanoscopic molecular motions into macroscopic deformation is the unique property of cross-linked liquid crystal polymers (CLCPs). These materials can directly transfer input light energy into mechanical work when combined with photochromophores, thus fascinating many scientists. This article reviews the macroscopic and microscopic deformation of photoresponsive azobenzene-containing CLCPs and analyses the influence of mesogen alignment and chemical structure on shape change behaviour. We highlight some new methods to trigger the deformation by visible and infrared light instead of ultraviolet one, such as chemical modification of azobenzene and addition of upconversion materials.

Biomimetic Submicroarrayed Cross-Linked Liquid Crystal Polymer Films with Different Wettability via Colloidal Lithography.

Photoresponsive cross-linked liquid crystal polymer (CLCP) films with different surface topographies, submicropillar arrays, and submicrocone arrays were fabricated through colloidal lithography technique by modulating different types of etching masks. The prepared submicropillar arrays were uniform with an average pillar diameter of 250 nm and the cone bottom diameter of the submicrocone arrays was about 400 nm, which are much smaller than previously reported CLCP micropillars. More interestingly, these two species of films with the same chemical structure represented completely different wetting behavior of water adhesion and mimicked rose petal and lotus leaf, respectively. Both the submicropillar arrayed film and the submicrocone arrayed film exhibited superhyrophobicity with a water contact angle (CA) value of 144.0 ± 1.7° and 156.4 ± 1.2°, respectively. Meanwhile, the former demonstrated a very high sliding angle (SA) greater than 90°, and thus, the water droplet was pinned on the surface as rose petal. On the contrary, the SA of the submicrocone arrayed CLCP film consisting of micro- and nanostructure was only 3.1 ± 2.0°, which is as low as that of lotus leaf. Furthermore, the change on the wettability of the films was also investigated under alternating irradiation of visible light with two different wavelengths, blue light and green light.

Dual-responsive inverse opal films based on a crosslinked liquid crystal polymer containing azobenzene

Novel photo and thermal dual-responsive inverse opal films were fabricated based on a crosslinked liquid crystal polymer (CLCP) containing azobenzene. Accompanying the deformation of the CLCP, switchable behavior on the reflection spectra of the inverse opal film was induced by light or temperature. We found that the optical properties were drastically decreased by thermal or photoinduced phase transitions of the CLCP. It was also found that the extent of decrease in the heat-induced inverse opal film is much more than in the one induced by light.

Visible Light Induced Bending Behavior of Crosslinked Liquid Crystal Polymers Containing Azotolane with a Longer Spacer

One azotolane-containing acrylate monomer with a longer spacer and a non-azotolane crosslinker were synthesized. Crosslinked liquid crystal polymer (CLCP) films were obtained by thermal polymerization of the mixture of the monomer and the crosslinker with a molar ratio of 2:8. Thermodynamic and mesomorphic properties of the monomer, the crosslinker and the CLCP films were characterized by DSC and POM. The CLCP films showed a low glass transition temperature which ensured them to bend at room temperature upon visible light irradiation. Besides, the films have a faster bending speed compared with the previously-reported azotolane-containing CLCP films with a shorter spacer.

Red-Light-Controllable Liquid-Crystal Soft Actuators via Low-Power Excited Upconversion Based on Triplet–Triplet Annihilation

A red-light-controllable soft actuator has been achieved, driven by low-power excited triplet-triplet annihilation-based upconversion luminescence (TTA-UCL). First, a red-to-blue TTA-based upconversion system with a high absolute quantum yield of 9.3 ± 0.5% was prepared by utilizing platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP) as the sensitizer and 9,10-bis(diphenylphosphoryl)anthracene (BDPPA) as the annihilator. In order to be employed as a highly effective phototrigger of photodeformable cross-linked liquid-crystal polymers (CLCPs), the PtTPBP&BDPPA system was incorporated into a rubbery polyurethane film and then assembled with an azotolane-containing CLCP film. The generating assembly film bent toward the light source when irradiated with a 635 nm laser at low power density of 200 mW cm(-2) because the TTA-UCL was effectively utilized by the azotolane moieties in the CLCP film, inducing their trans-cis photoisomerization and an alignment change of the mesogens via an emission-reabsorption process. It is the first example of a soft actuator in which the TTA-UCL is trapped and utilized to create photomechanical effect. Such advantages of using this novel red-light-controllable soft actuator in potential biological applications have also been demonstrated as negligible thermal effect and its excellent penetration ability into tissues. This work not only provides a novel photomanipulated soft actuation material system based on the TTA-UCL technology but also introduces a new technological application of the TTA-based upconversion system in photonic devices.

Light‐Switchable Behavior of a Microarray of Azobenzene Liquid Crystal Polymer Induced by Photodeformation

A microarray with a period of about 1 μm was fabricated from a crosslinked liquid crystal polymer (CLCP) containing azobenzene groups by using the replica molding technique. In accordance with the photoinduced deformation of the CLCP induced by the photoisomerization of the azobenzene groups, on-off switch behavior on the reflection spectra of the microarray was observed by alternate irradiation with UV-Vis light. The reversible switch behavior indicates that the azobenzene CLCP microarray has potential applications in optical actuators.

Crosslinked liquid crystal polymers from liquid crystal monomers: Synthesis and mechanical properties

AbstractDifunctional acrylates and methacrylate monomers have been made which are high order smectic liquid crystal (or crystalline) at room temperature. This report discusses materials with the following structure: F–S–M–S–F, where F is a functional group, acrylate or methacrylate (A or M); S is a spacer (CH2)n(n), and M is a mesogen—in this case 4,4′‐dioxybiphenyl (B). They are codified as BnA or BnM where n is the number of methylenes in the spacer. High conversion with high Tg can be obtained when polymerizing in the smectic state because the reactive end groups are concentrated in a small volume and can react well with little or no diffusion. B2A, B3A, B6A, B11A, and B3M were polymerized in the smectic state and compared to polymers made at temperatures where the monomers were isotropic. High conversion was obtained below final Tg—even then, probably because the polymers were ordered. All the polymers were studied by WAXD and dynamic mechanical spectroscopy. Solid‐state NMR on B3A showed that there was very high conversion of the double bonds at all temperatures. B3A photopolymerized in the smectic state (60–76°C) produced a crystalline polymer with Tg = 185°C (1 Hz). When photopolymerized at 85°C, above the isotropization temperature (Ti), a poorly organized polymer was obtained with a Tg of 155°C (1 Hz). Monomers with an odd number of methylene groups as spacers were crystalline after polymerization. With an even number of methylene groups, they lost most of their crystallinity on polymerization below Ti, but retained a low order smectic structure. Similar structures were obtained with all the monomers when they were polymerized above Ti. There was little effect of polymerization temperature on Tg when the spacers had an even number of methylene groups. © 1993 John Wiley & Sons, Inc.