Synthesis and properties of photoalignable aromatic polyesters containing phenylenediacrylate units in their backbones and n‐alkyl moieties in their side groups

A series of poly[oxy(4‐n‐alkyl‐3,5‐benzoate)oxy‐1,4‐phenylenediacryloyl]s (PPDA‐CnBZ polymers) with high molecular weights was synthesized. These polymers exhibit excellent solubility in some common organic solvents and produce good quality films using conventional spin‐casting and drying processes. The polymers are thermally stable up to 357–362 °C in a nitrogen atmosphere; their glass transition temperatures are greater than 121 °C. The photoreactions and photoalignments of the polymers were investigated using ultraviolet‐visible and infrared spectroscopy, and their liquid crystal (LC) alignment properties were examined. The phenylenediacrylate (PDA) chromophores in the polyesters were found to mainly undergo photocyclization upon ultraviolet light irradiation. Irradiation of the polyester films with linearly polarized ultraviolet light (LPUVL) induces preferential orientation of the polymer main chains, while the unreacted PDA chromophores are aligned along the direction perpendicular to the electric vector of the LPUVL. All the films irradiated with LPUVL were found to align LCs in a direction perpendicular to the electric vector of the LPUVL. Moreover, these LC alignments persisted even on irradiated films annealed at temperatures up to 210 °C, which is much higher than the glass transition temperatures of the polyesters. These LC alignment characteristics are due to the anisotropic interactions of the LC molecules with the oriented polymer chains and with the unreacted PDA chromophores. LC alignments on the polyester film surfaces have homeotropic to homogeneous characteristics, depending on the length of the n‐alkyl side group, providing strong evidence that the n‐alkyl side groups of the polyesters play a critical role in determining the pretilt angles of the LCs. The LC pretilt angles were also found to be influenced by the thermal annealing history of the irradiated films. In summary, the excellent properties of the PPDA‐CnBZ polymers make them promising candidate materials for use as LC alignment layers in advanced LC display devices. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1322–1334, 2004     

Photoalignment of liquid crystals by a covalently attached self-assembled ultrathin film

In this paper, the polyanion-containing cinnamoyl group (PACSS-CF3) was self-assembled with diazoresin (DR) to form a kind of stable covalent ultrathin film by irradiation with 365?nm UV light. The photoalignment properties of the DR/PACSS-CF₃ covalent film were investigated. The covalent film was found to have anisotropy after irradiation by 297?nm linearly polarised ultraviolet light (LPUVL), and could induce uniform alignment of liquid crystals (LCs). The pretilt angle of the LC was 2.5°. The stability of the film was enhanced by the covalent bonds. The films were thermally stable to 180°C. Polarised UV-Vis spectroscopy was utilised to investigate the photochemical process of the covalent film. It was found that cinnamoyl moieties parallel to the polarisation direction of the LPUVL were consumed by the photoreaction faster than those perpendicular to the polarisation direction. It can be concluded that the selective photoreaction induced the anisotropy of the films. The anisotropic films induced the homogeneous alignment of LC.     

Control of surface wettability and photomicropatterning with a polymorphic diarylethene crystal upon photoirradiation

A photochromic diarylethene crystal of 1,2‐bis(2‐methyl‐6‐nitro‐1‐benzothiophen‐3‐yl)perfluorocyclopentene ( 1 a ) was found to undergo a thermodynamic phase transition at 180 °C to form a needle‐like crystal, designated as 1 a‐γ . The phase transition involves melting of the initial α‐crystal and growth of the γ‐crystal. The phase transition temperature decreased with the presence of the closed‐ring isomer ( 1 b ) in the crystal because of the decrease in the melting temperature. Upon irradiation with ultraviolet (UV) light, compound 1 a in the α‐crystal was converted into 1 b to an extent of 20 %. Consequently, the α‐crystal containing 20 % of 1 b underwent the phase transition accompanied by melting of the crystal and growth of the γ‐crystal even at 170 °C. Photomicropatterning by the phase transition upon irradiation with UV light using a photomask, followed by heating at 170 °C, was successfully accomplished with a resolution in the microcrystalline pattern of about 20 μm. The contact angle with water on the γ‐microcrystalline phase on a glass substrate was larger than that on the α‐microcrystalline phase by 20°. This can be ascribed to a difference in the roughness of the surface. Furthermore, the γ‐microcrystal was also found to be formed upon heating an amorphous film of 1 a in poly(methyl methacrylate) for 2 min at 130 °C. The crystallized area exhibited a higher water contact angle than the amorphous area. Upon irradiation of the amorphous film with UV light, such crystallization did not take place because of the impurity effect of 1 b in 1 a . Photomicropatterning by the crystallization in the polymer showed a pattern with a higher resolution of about 4 μm, which was much better than that of the neat crystal. This photopatterning process represents a useful tool for controlling the surface wettability in relevant applications.     

Photomobile Polymer Materials: Photoresponsive Behavior of Cross‐Linked Liquid‐Crystalline Polymers with Mesomorphic Diarylethenes

Cross‐linked liquid‐crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross‐linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross‐linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed‐ring to open‐ring isomerization, the bent films revert to the initial flat state. Without visible‐light irradiation, the bent films remain bent even at 120 °C, indicating high thermal stability of the cross‐linked diarylethene LC polymers.     

Synthesis and characterization of novel polyimides containing stilbene unit in the side chain and their controllability of nematic liquid crystal alignment on the rubbed surfaces

Four polyimides containing hexylene spacer and a fluorostilbene unit in the side chains were prepared in thin‐film form by two‐step condensation of 3,3′‐bis[(4′‐fluoro‐4‐stilbenyl)oxyhexyloxy]‐4,4′‐biphenyldiamine (FS6B) with pyromellitic dianhydride (PMDA), benzophenone‐3,3′,4,4′‐tetracarboxylic dianydride (BTDA), 4,4′‐oxydi(phthalic anhydride) (ODPA), and 4,4′‐hexafluoroisopropylidenedi(phthalic anhydride) (6FDA), respectively, and their controllability of liquid crystal (LC) alignment on rubbed surfaces was investigated. Pretilt angles of LCs were achieved in the 2–9° range, depending on the rubbing density and backbone structures. The effect of the mesogenic stilbene group on the pretilting of LCs was distinctive in FS6B‐PMDA. Contact‐angle measurements on thin films annealed at 120 °C revealed that FS6B‐PMDA potentially had the better alignment stability than FS6B‐6FDA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3622–3632, 2001     

Preparation and photopatterning of Langmuir–Blodgett (LB) films of a novel copolymer containing swallow‐tailed double naphthalene groups

A new series of copolymer poly(N‐hexadecylmethacrylamide‐co‐dinaphthalen‐2‐yl 2‐allylmalonate) poly(HDMA‐co‐DNAM)s containing swallow‐tailed double naphthyl groups and long alkyl group were designed and synthesized. The behavior of copolymer molecular arranging on water surface, patterning properties of copolymer LB films, and photochemical reactions in ultrathin film were investigated. The poly(HDMA‐co‐DNAM)s could form a stable, well‐defined molecular orientation Langmuir monolayer at air/water interface. The polymer main chain was lying flat on water surface and the side chains attached to the main chain stretching out at the angle of about 50°. The results obtained showed that a well‐ordered layer‐by‐layer structure was successfully controlled in LB films, in which most of naphthyl groups in poly(HDMA‐co‐DNAM)s LB films were in dimer and the copolymer LB films were decomposed hardly upon irradiation of deep UV light. We found that the exposed and unexposed regions of the poly(HDMA‐co‐DNAM)s copolymer LB films had solubility differentiation in gold etchant, which is a mixed solution of I₂/NH₄I/C₂H₅OH/H₂O. Therefore, we could obtain gold photopattern with the maximal resolution of the employed mask without any development process. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and optical properties of novel blue‐light‐emitting poly(p‐phenylene vinylene) derivatives with pendant oxadiazole or cyano groups

Two novel poly(p‐phenylene vinylene) polymers, which carried side substituents with cyano groups or 1,3,4‐oxadiazole, were synthesized by Heck coupling. They consisted of alternating conjugated segments and nonconjugated aliphatic spacers. The polymers had moderate molecular weights, were amorphous, and dissolved readily in tetrahydrofuran and halogenated organic solvents. They were stable up to approximately 340 °C in N₂ and 290 °C in air, and the anaerobic char yield was around 60% at 800 °C. The polymer with cyano side groups emitted blue light in solutions and thin films with identical photoluminescence (PL) maximum at 450 nm; this supported the idea that chain interactions were hindered even in the solid state. The PL maximum of this polymer in thin films was blueshifted upon annealing at 120 °C, indicating a thermochromic effect as a result of conformational changes in the polymer backbone. The polymer containing side substituents with oxadiazole rings emitted blue light in solutions with a PL maximum at 474 nm and blue‐greenish light in thin films with a PL maximum at 511 nm. The PL quantum yields of the polymers in tetrahydrofuran were 0.13–0.24. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1768–1778, 2004     

Spin Self‐Assembled Clay Nanocomposite Passivation Layers Made from a Photocrosslinkable Poly(vinyl alcohol) and Na+‐Montmorillonite Enhance the Environmental Stability of Organic Thin‐Film Transistors

We investigated the effects of the multilayer polymer‐clay nanohybrid passivation films on the stability of pentacene organic thin‐film transistors (OTFTs) exposed to air and UV irradiation. Well‐ordered multilayer films were deposited by the spin‐assisted layer‐by‐layer assembly method using photocrosslinkable poly(vinyl alcohol) with the N‐methyl‐4(4′‐formylstyryl)pyridinium methosulfate acetal group (SbQ‐PVA) and Na⁺‐montmorillonite in a water‐based solution process. When photocrosslinked, these SbQ‐PVA/clay multilayers were found to serve as excellent barriers to O₂ and UV‐light. Moreover, when used as passivation layers, they enhanced the stability of pentacene OTFT devices exposed to air and UV radiation.     

Specular and Diffuse Reflectance of Phase‐Separated Polymer Blend Films

Diffuse reflectors have various applications in devices ranging from liquid crystal displays to light emitting diodes, to coatings. Herein, specular and diffuse reflectance from controlled phase separation of polymer blend films, a well‐known self‐organization process, are studied. Temperature‐induced spinodal phase separation of polymer blend films in which one of the components is selectively extracted is shown to exhibit enhanced surface roughness as compared to unextracted films, leading to a notable increase of diffuse reflectance. Diffuse reflectance of UV–visible light from such selectively leached phase‐separated blend films is determined by a synergy of varying lateral scale of phase separation (≈200 nm to 1 μm) and blend film surface roughness (0–40 nm). These critical parameters are controlled by tuning annealing time (0.5–3 h) and temperature (140, 150, 160 °C) of phase separation. Angle‐resolved diffuse reflection studies show that the surface‐roughened polymer films exhibit diffuse reflectance up to 40° from normal incident light in contrast to optically uniform as‐cast films that exhibit largely specular reflectance. Furthermore, the intensity of the diffusively reflected light can be enhanced (300–700 nm) or reduced (220–300 nm) significantly by coating the leached phase‐separated films with a thin silver over layer.

     

Synthesis and characterization of azo–bisbenzylidene‐based polymers for second order nonlinear optics

Main chain polymers containing azo and bisbenzylidene moiety were synthesized by polycondensation method. The successful polymerization reaction was characterized by UV–vis absorption, FT‐IR and NMR spectroscopy. The resulting polymers were soluble in polar solvents like dimethyl formamide (DMF) and showed good thermal stability up to 250 °C. These polymers were blended with poly methyl methacrylate (PMMA) and corona poled for characterizing second harmonic generation (SHG) property. Temperature stability study of SHG intensity of poled polymer showed that it is stable up to 80 °C. To improve temperature stability further the crosslinking of polymer under UV light is proposed. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4317–4324     

Highly efficient and stable blue‐light‐emitting binaphthol‐fluorene copolymers: A joint experimental and theoretical study of the main‐chain chirality

In a quest for the main‐chain chiral and highly stable blue‐light‐emitting π‐conjugated polymers, a novel series of soluble conjugated random and alternating copolymers (PF‐BN) derived from fluorene and axially chiral 1,1′‐binaphthol (BINOL) were successfully synthesized by Suzuki coupling polymerization. The polymer structures, optical properties, and their electrochemical properties were investigated by ¹H NMR, TGA/DSC, UV‐Vis absorption, photoluminescence, cyclic voltammetry, circular dichroism spectroscopy, and DFT calculations. The blue‐light‐emitting BINOL‐containing copolymers with proper content of BINOL show highly efficient photoluminescence and ultra highly stable light‐emission with almost unchanged fluorescent spectra after annealing at 200 °C in air for 10 h. The joint experimental and theoretical study of the main‐chain chirality reveals that (1) the chirality of BINOL can be transferred to the polymer backbone, (2) the effective conjugation length is about one BINOL and three fluorenes, (3) the main active chiral block in the copolymers is probably composed by one BINOL with the other two or three fluorenes, and (4) the dihedral angle in the PF‐BN copolymers should be larger than 105°. The incorporation of BINOL into the polyfluorene backbone is an effective way to produce highly efficient and stable blue‐light‐emitting main‐chain chiral conjugated polymer with interesting optoelectronic properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3868–3879, 2010     

UV dosimeters based on neotetrazolium chloride

A novel UV dosimeter is described comprising a tetrazolium dye, neotetrazolium chloride (NTC), dissolved in a film of polymer, polyvinyl alcohol (PVA). The dosimeter is pale yellow/colourless in the absence of UV light, and turns red upon exposure to UV light. The spectral characteristics of a typical UV dosimeter film and the mechanism through which the colour change occurs are detailed. The NTC UV dosimeter films exhibit a response to UV light that is related to the intensity and duration of UV exposure, the level of dye present in the films and the thickness of the films themselves. The response of the dosimeter is temperature independent over the range 20–40 °C and, like most UV dosimeters, exhibits a cosine-like response dependence upon irradiance angle. The introduction of a layer of a UV-screening compound which slows the rate at which the dosimeter responds to UVR enables the dosimeter response to be tailored to different UV doses. The possible use of these novel dosimeters to measure solar UV exposure dose is discussed.     

Syntheses and alignment behavior of liquid crystalline polymethacrylates having 2‐ and 4‐styrylpyridine moieties

Two kinds of polymethacrylates, 1 and 2 , with 2‐styrylpyridine and 4‐styrylpyridine moiety as a photoreactive group, which have a benzoate group as a mesogenic unit, and hexylene group as a flexible spacer in the same side chain, were synthesized to characterize their alignment behaviors. The UV absorption and fluorescence studies on the two polymers revealed that the latter polymer with the 4‐stylrylpyridine moiety is more aggregative than the former polymer with the 2‐styrylpyridine moiety. The polymer 1 showed a nematic phase structure at 170 °C, while 2 appeared in a partially bilayered smectic A phase structure in the homeotropic direction at 175 °C. The polymer 1 film generated an in‐plane alignment by a linearly polarized UV light irradiation and subsequent annealing, and its direction was parallel with respect to the irradiation. On the other hand, the polymer 2 film with the same treatments gave a high out‐of‐plane order parameter of 0.73 in a wide temperature range of 120–240 °C. The significant differences in the aggregation behavior, the liquid‐crystalline structure, and the alignment between the two polymers were discussed by the structural differences between the 2‐ and 4‐styrylpyridine moieties in the two polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5371–5380, 2008     

The effect of polymerizable surfactants on morphology and electro-optical of PDLCs films based on epoxy acrylate system

Polymer dispersed liquid crystals (PDLCs) have been extensively studied for various excellent electro-optical applications. The anchoring interaction of liquid crystals (LCs) molecules on the surface of the polymer cavity surrounding an LCs droplet has a crucial effect on the electro-optical performance of the PDLCs. The effect of polymerizable surfactants on the electro-optical properties of PDLCs films was studied in detail. The active double bonds were polymerized with prepolymer to stabilize the performance of polymer matrix. The experimental results showed that polymerizable surfactants could effectively reduce the driving voltage. The speed of polymerization was monitored by real-time transmittance. The electro-optical properties of PDLC films were measured by Polarimeter (PerkinElmer Model 341). The driving electric field was reduced from 3.9 V/μm to about 2.8 V/μm for doping undec-10-enoic acid at curing temperature 80?°C. The surfactants containing polymerizable functional groups, polarity, and alkyl chain weakened the surface anchoring between LCs droplets and polymer interface. The morphologies of PDLCs films were also investigated by polarizing optical microscopy (POM) and Fourier transform infrared (FTIR) images. The LC droplets were encapsulated by polymerizable surfactant according to FTIR images.     

Optical activity of chiral thin film and liquid crystal hybrids

Using the glancing angle deposition (GLAD) technique, we have fabricated porous, chiral thin films with optically anisotropic helical microstructures that exhibit optical phenomena such as wavelength specific rotation of linearly polarized light. Initial research has shown that the porosity of the films allows for the addition of nematic liquid crystals (NLCs) to the films for promising applications in dynamically switchable devices, while simultaneously enhancing the optical properties of the film. This study describes the fundamental optical behaviour of LC-filled chiral thin films in relation to material, porosity, structure and thickness. It was found that for SiO₂ films, the addition of NLCs increased the effective rotatory power by two-fold when compared with results from the film without added LCs. The rotatory power of Al₂O₃ and MgF₂ films, while being similarly increased by the addition of LCs, exhibited a reversal in sign, or direction of rotation, for the visible wavelength spectrum investigated. The effects of film porosity and structure were studied by varying the angle of incidence from 83° to 86°; it was found that the greater porosity of the films deposited at larger angles allowed for more filling by the LCs and thus a larger increase in rotatory power. Finally, the addition of LCs was observed to shift the wavelength of peak rotation towards smaller values.     

Linearly polarized ultraviolet photoreaction of photocrosslinkable polymers comprising the p-phenylenediacrylate group and photoalignment control of liquid crystals on the resultant film

We present (1) the linearly polarized (LP) ultraviolet (UV) photoreaction of block copolyesterethers comprising a hard segment of polyester and soft segment of poly(tetramethylene ether) (PTMG) and (2) the alignment behavior of liquid crystals (LCs) on the resultant photoreacted polymer films. Two kinds of copolyesterethers with different polyester segments of poly(hexamethylene p-phenylenediacrylate) (1a) or poly(hexamethylene p-phenylenediacrylate)-co-poly(hexamethylene 1,4-dibenzoate) (1b) were used in this study. The LP–UV irradiation resulted in a negative optical anisotropy for both polymer films, and a homogeneous photoalignment of LCs was achieved on the photoreacted polymer film. The LC alignment was perpendicular to the electric vector of the incident polarized light for 1a, whereas a reversion of the alignment from parallel to perpendicular was observed for 1b, depending on the irradiation doses. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4000–4006, 1999     

Suppressing pretilt angle for enhancing black quality in diagonal viewing angle of homogenously aligned liquid crystal display

The diagonal viewing angle light leakage in a black state of in-plane switching (IPS) liquid crystal display (LCD) associated with pretilt angle has been investigated. The mechanical rubbing process with a cloth causes relatively high pretilt angle in the homogenously aligned liquid crystals (LCs) so that the tilted LC director results in increase of a light leakage in a black state at diagonal viewing angles. In this study, we theoretically estimated using classical optic theory how the light leakage in a black state at diagonal viewing angle is associated with the pretilt angle and also proposed an effective method to reduce the pretilt angle from 1.5° to 0° in rubbed IPS LCD by utilising polymer stabilisation. With this approach, we could successfully acquire a better black quality in all viewing angles as compared with normal IPS LCD.     

Poly(arylene sulfide)s by nucleophilic aromatic substitution polymerization of 2,7‐difluorothianthrene

Poly(thianthrene phenylene sulfide) and poly(thianthrene sulfide) have been prepared by nucleophilic aromatic substitution polymerization of the activated monomer 2,7‐difluorothianthrene with bis thiophenoxide and sulfide nucleophiles, respectively. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) mass spectrometry, UV‐Vis spectroscopy, refractometry, and intrinsic viscosity (IV) measurements. The polymers produced exhibit 5% weight loss values approaching 500 °C in inert and air atmospheres and glass transition temperatures that range from 149 to 210 °C. Poly(thianthrene phenylene sulfide) with a number average molecular weight of 22,100 g/mol has been synthesized with an IV in DMPU of 0.62 dL/g at 30 °C. Creasable films of this polymer have been prepared by solvent casting and melt pressing at 250 °C. Films of poly(thianthrene phenylene sulfide) exhibit transparencies greater than 50% at wavelengths exceeding 400 nm and a high refractive index value of 1.692 at a wavelength of 633 nm, making the polymer interesting for optical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2453–2461, 2009     

The fabrication of novel optical diffusers based on UV-cured polymer dispersed liquid crystals

Polymer dispersed liquid crystals (PDLCs) with different sizes of the LC droplets are prepared based on the ultraviolet (UV) light curable acrylate monomers/LCs composites to fabricate the optical diffuser films. To acquire light diffusers with high optical performance, the effects of the monomer structure and the UV light intensity on the micro-structure of the PDLC films are studied. Results show that the PDLC films could exhibit a strong light scattering at the premise of maintaining high transmittance in the visible region. As the LC droplets are spherically dispersed in the polymer networks, when the size of LC droplets is about 3.0 μm, the haze can reach 88.5% and the transmittance is nearly 90.0%, which can be used as a bottom diffuser film. While when the size of LC droplets is about 10.0 μm, the haze and transmittance are 39.2% and 90.2%, respectively; hence, it can be a good choice for a top diffuser film. With the advantages of simple preparation, roll-to-roll industrial production and tunable optical properties, it is supported that the films based on UV-cured PDLC films can be applied as outstanding optical diffuser films in the liquid crystal display industry.     

Surface‐attached polymer networks through carbene intermediates generated from α‐diazo esters

We report on the generation of surface attached polymer networks through C,H insertion reactions based on carbene intermediates. To this copolymers based on N,N‐dimethyl acrylamide, which contain α‐diazo ester groups, are generated and coated onto a solid substrate covered with a self‐assembled monolayer of a silane. After deposition, films having thicknesses of approximately 120 nm are irradiated with UV light having a wavelength of 254 nm or 360 nm or heated to temperatures between 80 and 180 °C. During the light or heat‐induced activation process, carbenes are formed, which react via C—H insertion with any neighboring polymer chain and/or with the self‐assembled monolayer on the substrate, thus forming surface‐attached polymer networks. To follow the kinetics of the crosslinking process, the conditions are adjusted, so that they range between 5 and 10 min for the UV‐crosslinking and 5 to 15 min for the heat‐induced crosslinking. UV‐patterning of the surface‐attached polymer networks through chrome contact masks allows generation of microstructures in the micrometer range. We investigate the layer formation process and describe the formation of microstructured surfaces based on these surface‐attached polymer networks. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3276–3285