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1.
Effects of copolymer composition on morphology and electrooptical properties of polymer/liquid crystal (LC) (40/60 w/w) composite films were studied with styrene-co-acrylonitrile (SAN) of varying acrylonitrile (AN) content (6.3–35 wt %) and a cyanobiphenyl-type liquid crystal (E8). The dimension of the LC domain in the composite film decreased with increase of AN content of SAN up to 30 and increased at 35 wt %. The contact angle of the film with an LC drop showed a similar trend; however, its minimum was obtained at 24% AN. Threshold voltage (Vth) and rise time (τR) increased, and decay time (τD) decreased with AN content up to 30%, and the tendency is reversed at 35%. The results were interpreted in terms of, possibly, a solubility parameter matching between SAN and LC. © 1993 John Wiley & Sons, Inc.  相似文献   

2.
Polymer‐dispersed liquid crystals (PDLCs) have garnered significant interest and motivated the investigation of the phase behavior of thermally stable smectic liquid crystals (LCs) via thermally induced phase separation (TIPS). In this study, we examined a series of two, biphenyl‐based smectic LCs suitable for high temperature polymer blend processing. Phase diagrams for LC/polystyrene (PS) blends at various compositions (0–60 wt%) were constructed. Less than 15 wt% of 8B8 (1,1′‐biphenyl‐4,4′‐diyl dioctanoate) LC in PS led to good polymer miscibility, while phase separation was induced at concentrations higher than 15 wt%. The LC concentration at saturation decreased with increasing aliphatic chain length. We also investigated the chain length (C6‐C16) effect on the PS glass transition temperature (Tg) at the LC saturation point. The Tg increased with increasing chain length due to reduced plasticization. We further examined the role of chemical structure (relatively less polar ether vs. more polar ester) on the phase diagram regions and the Tg of the nonpolar PS matrix, respectively. It is anticipated that these LC/PS phase diagrams will benefit elevated temperature processing for TIPS by highlighting the role of LC chemical structure and chain length on blend morphology. POLYM. ENG. SCI., 56:388–393, 2016. © 2016 Society of Plastics Engineers  相似文献   

3.
The photodegradation of copolyesters based on 1,4-cyclohexanedimethanol (CHDM), tetramethyl-1,3-cyclobutanediol, and terephthalic acid units was investigated using various analytical methods. Photodegradation products were characterized using Fourier transform infrared (FTIR), liquid chromatography–mass spectrometry (LC–MS), and X-ray Photoelectron spectroscopy (XPS) analysis. The homolytic scission of C-O bonds of ester groups through a Norrish Type I reaction was supported by time of flight secondary ion mass spectrometry and LC–MS results, while nuclear magnetic resonance analysis confirmed hydrogen abstraction from the tertiary carbon of CHDM units in the trans (equatorial-equatorial) conformation. Chain scission through Norrish Type II reaction is also responsible for the formation of carboxylic acid end group. Fluorescence emission from irradiated glycol modified poly(ethylene terephthalate) films demonstrated the formation of mono- and dihydroxyterephthalate species. Furthermore, FTIR and XPS valence band analysis confirmed configurational changes, in the polymer chain due to photodegradation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47148.  相似文献   

4.
A novel carbazole–triphenylamine copolymer‐bearing pendant bipyridine PM1TPA and corresponding europium (III) complexed polymer PM1TPA–Eu–x, in which the values of x are 0.1, 0.5, and 1.0 representing the molar ratio of bipyridine ligands complexed with Eu(III), were designed and synthesized. Their chemical structures were confirmed by 1H NMR, FT‐IR, and elemental analysis. Both PM1TPA and PM1TPA–Eu shows good solubility in common organic solvents such as tetrahydrofuran (THF) and CHCl3. The 5% weight loss temperature (Td5%) of PM1TPA and PM1TPA–Eu–1.0 are 363oC and 306oC, respectively. The photoluminescence (PL) spectra of PM1TPA–Eu in solution consists of two emission bands, one in the 400–570 nm region and another at 612 nm, corresponding to the emission of polymer main chain and europium complexes, respectively. When the concentration of PM1TPA–Eu–1.0 in THF solution increases, the PL intensity in the 400–570 nm regions became more and more weaker. And only the characteristic emission of europium complex was observed in the solid film, which indicates that the excited energy absorbed by the polymer backbone was efficiently transferred to the europium complexes. Furthermore, nearly monochromatic red electroluminescence from europium complex was observed from the polymeric light‐emitting diode using PM1TPA–Eu–1.0 as the emissive layer under 25 V forward bias. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42746.  相似文献   

5.
Poly(alkenoic acid)s constructed with β‐alanine and glutamic acid were synthesized and grafted with glycidyl methacrylate (GM). The purified polymers were further formulated with water, acrylic acid (AA), and Fuji II LC glass filler to form photocurable dental cements. Compressive strength (CS) and flexural strength (FS) of the cement, and viscosity of the resin liquid were used as screening tools to find the optimal formulation. The specimens were conditioned in distilled water at 37°C for 24 h, prior to testing. The results show that the effects of grafting ratio, polymer content, powder liquid (P/L) ratio, initiator concentration, and light exposure time were significant, but the effect of molecular weight was not. Aging study shows that the experimental cement showed a constant increase in mechanical strength for up to 1 week and then kept constant over 1 month. The formulation with 50/25/25 (liquid composition of polymer/AA/water), 70% (grafting ratio of GM), 3.2/1 (P/L ratio) as well as 0.9% (camphorquinone) and 1‐min light exposure time were found to be the optimal. The experimental cement was 19% higher in CS, 47% higher in diametral tensile strength and 176% higher in FS, compared to Fuji II LC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1587–1595, 2007  相似文献   

6.
A series of triarylaminooxadiazole‐containing tetraphenylsilane light emitting polymer (PTOA) and poly(2‐methoxy, 5‐(2′‐ethyl‐hexyloxy)‐p‐phenylene‐vinylene) (MEH‐PPV) based white light emitting polymer devices (PLEDs) were fabricated to study blue and orange–red emitter composition and light emitting layer processing effects on white emission electroluminescence properties. Color purity, current turn‐on voltage, brightness, and current efficiency were strongly determined by MEH‐PPV content and the thin film processing condition. The intensity of PTOA blue emission was equal to that of MEH‐PPV orange–red emission when the device was fabricated by a polymer composite film containing 10 wt % of MEH‐PPV. Color purity [Commission Internationale de L'Eclairage (CIEx,y) coordinates (0.26,0.33)] was nearly white emission under applied 8 V. The brightness and current efficiency of PTOA‐MEH‐PPV composite film based devices increased as MEH‐PPV content increased. Furthermore, white emission blue shifted with increasing spin‐rate of thin film coating and applied voltage. Low turn‐on voltage, high current density, and high brightness were obtained for the device fabricating with light emitting layer coating with high spin‐rate. Moreover, low current efficiency was obtained for the PLED with a thinner light‐emitting layer. A white emission CIE (0.28,0.34) was obtained for PTOA‐MEH‐PPV based white PLED. White PLED brightness and efficiency can be as high as 700 cd/m2 and 0.78 cd/A, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

7.
The textural and electrooptical behavior of a nematic liquid crystal (LC) dispersed in a flexible and rigid polyester was studied. The dispersion of LC in the polymer matrix and light transmission through the polymer‐dispersed liquid crystal (PDLC) is governed by the nature of the polymer, its molecular weight, and the applied voltage. It was observed that the transmission of light and the dispersion of LC maximizes their respective values at the minimum molecular weight irrespective of the nature of the polymer and at the maximum voltage. The reason is the predominance of chain alignment over entanglement at the minimum molecular weight. As molecular weight increases, the transmission of light as well as the dispersion of LC in the polymer may increase or decrease depending on the predominance of chain entanglement or chain alignment. The alignment of LC droplets in the direction of the applied voltage is increased by an increase in the applied voltage, causing enhancement of the light transmission. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 284–289, 2003  相似文献   

8.
ABA‐type block copolymers composed of 2,5‐diphenyl‐1,3,4‐thiadiazole (DPTD) oligoester and poly(methyl methacrylate) (PMMA) segments (Mn = 16 200 and 23 000) were synthesized by atom‐transfer radical polymerization and their liquid‐crystalline (LC) and photoluminescence (PL) properties were examined. The structures of block copolymers were identified by Fourier transform infrared and 1H NMR spectroscopies. Differential scanning calorimetry measurement, polarizing microscopy observation and wide‐angle X‐ray analysis revealed that the block copolymers form thermotropic LC phase (smectic C) independent of molecular weights of PMMA segments, but a model polymer (PMMA segments having the DPTD unit in the central part) has no LC melt. Solution and solid‐state PL spectra indicated that all the block copolymers display blue emission arising from the DPTD unit. Their quantum yields are 17–21%, which increase with the PMMA chain lengths. The block copolymers have good aligned structures in the LC states, but their order parameter (S) values in sheared LC states were lower than those in the sheared LC compounds. The PL properties in the LC states were independent of the LC aligned structures. Cyclic voltammetry measurements showed that these block copolymers have deep HOMO levels compared with polymers composed of oxadiazole rings. Copyright © 2007 Society of Chemical Industry  相似文献   

9.
Summary A new class of soluble poly(p-phenylenevinylene)-modified conjugated polymers with a simple aromatic unit of 3,4-bis(phenylene)-3-cyclobutene-1,2-dione in the main chain was synthesized by the dehalogenation polycondensation and the Heck reaction. The monomer and the polymers were characterized by FT-IR, 1H-NMR, UV-visible, Elemental Anaylsis, TGA and DSC. The resultant polymers were obtained as yellow powder, formed the brittle film from the DMAc solution. These polymers were soluble in polar aprotic solvents, such as NMP, DMAc, DMF and DMSO. The present polymers show absorption bands in the range of 286∼325nm, corresponding to the π-π* electronic transition of the conjugated polymer backbones. The photoluminescence spectrum of the polymer 1 shows a peak at 471nm while the polymer 2 has the peak at 522nm with DMAc solution, in the blue emission region. Received: 21 January 1999/Revised version: 2 April 1999/Accepted: 5 April 1999  相似文献   

10.
A series of azobenzene monomers and related model compounds with various side‐chain lengths were synthesized. The electrooptical properties of a polymer‐dispersed liquid crystal (PDLC) were verified by side‐chain methoxy azobenzene in various chain lengths (n = 3, 6, 11). The properties under various voltages were measured and the effect of extra voltage on the transmittance of PDLC was researched as well. The experiment demonstrated the validity of employing these side chain methoxy azobenzene materials in electrooptical devices. The azobenzene model compound showed better electric–optical and thermal–optical properties, having a higher contrast ratio (CR = 689) and a lower saturation voltage (4.7 V/μm). All the azobenzene molecules can be photoisomerized through UV light irradiation, following the mechanism of isomerization. The reversible photo and heat isomerization property was studied. The cis‐azobenzene that was transformed from the trans‐azobenzene irradiated by UV light can decrease the clearing point of the liquid crystal phase. We used this unique characteristic to record image patterns and it worked successfully. We synthesized the azobenzene monomers can stabilize the PDLC and their relative model compounds with various alkyl chain lengths even got better electric–optical effects. We found that azobenzene monomer shows different behaviors in the electric–optical property from its relative model compound. The difference between the systems were explained using a proposed model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 721–732, 2005  相似文献   

11.
The liquid crystal display (LCD) technology is confronted with the task to substitute rigid glass plates enclosing the electro‐optically active liquid crystal (LC) material by plastic substrates. In particular, the commercialization of flexible displays requires a sufficient stabilization against external mechanical distortions. To achieve LC layer stabilization, several procedures have been suggested. In this work, the thermal‐induced phase separation (TIPS) technique has been applied to generate composite films consisting of LC compartments which are encased by coherent polymer walls after binodal phase separation. Composite films were prepared from a series of poly(methacrylates) and various commercial nematic LC mixtures. Furthermore, the use of copolymers as well as binary blends from “hard” and “soft” poly(methacrylates) broadens the possibilities to control the film morphology. To compare different polymer/LC composite films regarding their stability under compression load, the samples were investigated by indentation tests using an inverse reflected‐light microscope combined with a digital image acquisition technique. The deformation of the composite layers was evaluated by the uniDAC image analysis which relies on the more general method of Digital Image Correlation (DIC). Some of the fabricated composites show a remarkably high indentation resistance, especially such prepared from poly(1‐tetralyl methacrylate) and poly(4‐tert‐butylcyclohexyl methacrylate). The results facilitate the selection of suitable composite systems for the fabrication of mechanically stabilized flexible LC displays. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

12.
Abstract

Blends of poly(ethylene terephthalate) (PETP) and two different thermotropic liquid crystalline (LC) polymers of the Vectra-type were prepared by melt mixing. Oxygen and water vapor permeability, light transmission and welding properties were measured on compression-molded and film-blown specimens. SEM showed that the LC polymers were the disperse phase with a good phase adhesion to the PETP matrix in the majority of the compression-molded blends. The 50/50 blend based on the low melting point LC polymer showed possibly a continuous LC polymer phase. The film-blown specimens showed LC polymer spheres at low LC polymer content. Above a certain LC polymer content (10-30% LC polymer), fibrous and ellipsoidal LC polymer particles was the dominant morphological feature of the blends. Density measurements showed that the void content in the blends was low. The compression-molded blends based on the high melting point LC polymer showed permeabilities conforming to the Maxwell equation assuming low permeability (LC polymer) spheres in a high permeability (PETP) matrix. The compression-molded blends based on the low melting point Vectra showed lower permeabilities than predicted by the Maxwell equation, particularly at high LC polymer content. The film-blown blends showed extensive scattering in the permeability data. The blend with 30% low melting LC polymer exhibited a 96% lower oxygen permeability than PETP. This was due to a reduction in both oxygen diffusivity and solubility. Ellipsoidal and fibrous LC polymer particles increased the diffusional path and lowered the diffusivity. The transparency of the compression-molded samples was lost already at 1% LCP. The blends showed welding properties superior to those of PETP.  相似文献   

13.
The liquid‐crystalline (LC) monomer 4‐allyoxybenzoyloxy‐4′‐buthylbenzoyloxy‐p‐phenyl (M1), whose LC phase appeared at lower temperatures, from 137 to 227°C, and the modified mesogenic monomer 4‐allyoxybenzoyloxy‐4′‐methyloxybenzoyloxy‐p‐biphenyl (M2), whose LC phase appeared at higher temperatures, from 185 to 312°C, were prepared. A series of side‐chain LC polysiloxanes containing M1 and M2 were prepared by graft copolymerization. Their LC properties were characterized by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction. The results show that the introduction of the modified mesogenic monomer M2 into the polymeric structure caused an additional increase in the clearing point (isotropic transition temperature) of the corresponding polysiloxanes, compared with unmodified polysiloxanes, but did not significantly affect the glass‐transition temperature. Moreover, the modified polysiloxanes exhibited nematic phases as the unmodified polymer did. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1196–1201, 2005  相似文献   

14.
In order to obtain amorphous thin films of a polydiacetylene, a polyisophthalate containing a push–pull diacetylene chromophore was synthesized by the reaction of p-(N,N-diethanolamino)-p’-nitrodiphenylbutadiyne with isophthaloyl chloride in anhydrous 1-methyl-2-pyrrolidone. The polymer was soluble in organic solvents, such as chloroform, tetrahydrofuran, dimethylformamide, etc., and films with good optical quality were obtained by spin coating from its N-methyl-2-pyrrolidone solution. It was characterized by 1H-NMR, IR, DSC, UV–Visible, X-ray, etc. The diacetylene groups underwent polymerization in the film when irradiated with UV light at 120 °C under Ar atmosphere, and it contained free radicals with a radical concentration of 1016 radicals/g. The third-order nonlinear optical susceptibility, χ(3), of the polymer film measured by the Z-scan technique at 1064 nm was not noticeable, but when the film was heated and irradiated with UV light, a χ(3) value of 6.4?×?10?10 esu was obtained due to increase in π-conjugation by the formation of polydiacetylene in the side chain.  相似文献   

15.
The dynamic mechanical behaviour of random copolymers of LC monomer-1-(hexyloxycarbonyl)ethyl 4-[4-(methacryloyloxy)benzoyloxy]benzoate (HB) and octyl methacrylate (OMA) was studied in the main transition and flow regions. Even though the aliphatic end groups of the side chain of HB and OMA are roughly the same, the T g temperature of poly(HB) is ∼ 80 K higher than that of poly(OMA); this fact is due to the presence of the stiff phenyl benzoate mesogenic group in the side chain of HB. With increasing content of OMA in the copolymer the superimposed curves of the storage G′ p and loss G′′ p moduli at a constant temperature shift towards shorter frequencies. It has been shown that this shift is mainly due to an increase of the free volume in the copolymers with increasing content of OMA. While HB monomer shows liquid crystalline (LC) properties, its polymer (poly(HB)) and random copolymers with OMA show only isotropic thermal behaviour because no flexible spacer is present in the side chain of HB which would decouple the main chain and mesogenic group motions. This means that neither the homopolymer of HB, nor its copolymers with a flexible comonomer retain the LC properties of the starting LC monomer, HB. Received: 26 September 1996/Revised: 7 November 1996/Accepted: 7 November 1996  相似文献   

16.
A novel series of well‐defined alternating poly[2,7‐(9,9‐di(2‐ethylhexyl)fluorenyl)‐alt‐pyridinyl] (PDEHFP) copolymers were synthesized using palladium(0)‐catalyzed Suzuki coupling reaction in high yields. These polymers were characterized using 1H NMR, UV‐visible and fluorescence spectroscopies, gel permeation chromatography, thermal analysis and cyclic voltammetry. The optical properties of the copolymers, including photoluminescence (PL) and electroluminescence (EL), were studied. The difference in linkage position of pyridinyl units in the polymer backbone has significant effects on the electronic and optical properties of polymers in solution and in film state. Meta‐linkage (3,5‐ and 2,6‐linkage) of pyridinyl units in the polymer backbone is more favorable for pure blue emission and prevention of aggregation of polymer chains. PDEHFPs with 2,6‐ and 3,5‐linkage of pyridinyl units have relatively high PL efficiency of 37 and 44% in the film state. In comparison with homopolymer PDEHF, the copolymers with pyridinyl units possess low lowest unoccupied molecular orbital energy levels for easy electron injection from a cathode. Strong EL is observed and light‐emitting diodes (LEDs) exhibit typical rectifying characteristics. The emission intensity starts to increase at around 12 V. The emission peak wavelengths of the polymers roughly coincide with those of PL. This series of fluorene–pyridine‐based alternating copolymers seem to be candidates for polymeric LEDs. © 2013 Society of Chemical Industry  相似文献   

17.
A blue light‐emitting statistical poly(p‐phenylenevinylene) (PPV) copolymer with hole‐transporting carbazole and electron‐transporting oxadiazole pendant groups attached to the kinked m‐terphenyl unit was prepared by Heck coupling between 1,4‐divinylbenzene and dibromides. The latter were synthesized through pyrylium salts. The polymer had optical band gap of 2.89 eV and emission maximum at 446 nm in THF solution and 434 nm in thin film. It showed a pure blue emission with no aggregates or excimers formed even in solid state because of the long and bulky pendant groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3842–3849, 2006  相似文献   

18.
Current progress in the synthesis and properties of conjugated polymers is presented by focusing on recently put forward hyperstructured helical polyacetylene. Interfacial polymerization of acetylene has been carried out in an asymmetric reaction field consisting of chiral nematic liquid crystal (N*‐LC) and Ziegler–Natta catalyst. Since the chiral nematic liquid crystal is composed of nematic liquid crystal and a chiral compound such as axially chiral binaphthyl derivative with R‐ or S‐configuration, the screw directions of the polyacetylene chain and fibril bundle and even the spiral morphology are rigorously controlled by selecting the chirality of the chiral compound. Surprisingly, the screw directions of the fibril and the bundle of fibrils in helical polyacetylene were found to be opposite to that of N*‐LC. It is worthwhile to emphasize that the hierarchical spiral morphology involving the primary to higher order structure is generated in a synthetic polymer such as polyacetylene by using N*‐LC as an asymmetric polymerization solvent. Copyright © 2007 Society of Chemical Industry  相似文献   

19.
Liquid crystalline (LC) alkyd resins with mesogenic side chains are prepared with the following three methods: (a) grafting p-hydroxybenzoic acid (PHBA) to hydroxy-terminated alkyd resin, (b) grafting PHBA to carboxyl-terminated alkyd resin, and (c) grafting PHBA to an excess succinic anhydride-modified alkyd resin. Dicyclohexylcarbodiimide (DCC) is employed to react with formed water in promoting esterification of PHBA with alkyd at room temperature. Pyridine is used as a solvent, and the catalytic amounts of p-toluene-sulfonic acid (p-TSA) is added to suppress side reaction and to promote esterification. Grafting efficiency (% GE) is estimated to range from 70 to 95%. The character of liquid crystallinity is imparted only when at least two or more aromatic units of PHBA are connected to form the rodlike mesogenic side chain. At present, we have found that LC alkyd resins have the following merits: the polymer solution viscosity is reduced; the coating's dry-to-touch time is reduced; and the coating film is both hardened and toughened and has excellent resistance to water and acid. © 1992 John Wiley & Sons, Inc.  相似文献   

20.
Two new thiophene‐based donor–acceptor (D–A) conjugated polymers, PDTOFV and PDTOCN, are synthesized and characterized. The polymers are readily soluble in common organic solvents and exhibit good thermal stability with onset decomposition temperature (Td) in the range 310?330°C. Cyclic voltammetry studies revealed that polymers possess low‐lying highest occupied molecular orbital (HOMO) energy levels (?5.94 eV for PDTOFV and ?5.86 eV for PDTOCN) and low‐lying lowest unoccupied molecular orbital (LUMO) energy levels (?3.35 eV for PDTOFV and ?3.55 eV for PDTOCN). The optical band gap is calculated from onset absorption edge of the polymer film. The polymers exhibit green fluorescence with fluorescence quantum yields (?fl) of 38% and 42%, respectively, for PDTOFV and PDTOCN. Polymer light‐emitting diodes (PLEDs) are fabricated using these polymers with a device configuration of ITO/PEDOT:PSS/polymer/Al. The device based on PDTOFV emitted green light with Commission Internationale de I'Eclairage (CIE) coordinate values of (0.25, 0.39). Whereas, the device based on PDTOCN showed white light emission with CIE coordinate values of (0.32, 0.35), which is very close to the values (0.33, 0.33) of standard white light emission. The threshold voltages of the PLEDs are determined by current density‐voltage characteristics and are found to be 7.3 and 3.9 V for PDTOFV and PDTOCN, respectively. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

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