Investigation of electro-optical characteristics of photo-aligned TN-LCDs on PCEMA surfaces

In this work, a novel photo-alignment material, poly(cinnamolyethyl methacrylate) (PCEMA), was synthesized by photo-dimerization. We investigated the electro-optical characteristics of twisted nematic (TN)-liquid crystal displays (LCDs) photo-aligned with linearly polarized UV light irradiation at normal direction on the PCEMA surfaces. Excellent voltagetransmittance characteristics were observed. The threshold voltage of the photo-aligned TN-LCD decreases with increasing UV irradiation time. Additionally, response times are almost the same as for a rubbing-aligned TN-LCD.     

Effects of the cinnamoyl group on liquid crystal aligning capabilities on PCEMA surfaces

Four kinds of poly(4-methacryloyloxychalcone) (PCEMA) photo-alignment materials were synthesized. The effect of the cinnamoyl group on liquid crystal (LC) aligning capabilities and electro-optical characteristics of photo-aligned twisted nematic (TN) liquid crystal displays (LCDs) was investigated by photo-dimerization. Uniform NLC alignment by linearly polarized UV exposure at normal incidence on the PCEMA surfaces having a high density of cinnamoyl groups was observed. Also, excellent voltage-transmittance (V-T) curves for the photo-aligned TN-LCDs on the PCEMA surfaces was achieved. We find that the V-T and response time characteristics can be improved by increasing the density of cinnamoyl groups.     

Effects of the cinnamoyl group on liquid crystal aligning capabilities on PCEMA surfaces

Four kinds of poly(4-methacryloyloxychalcone) (PCEMA) photo-alignment materials were synthesized. The effect of the cinnamoyl group on liquid crystal (LC) aligning capabilities and electro-optical characteristics of photo-aligned twisted nematic (TN) liquid crystal displays (LCDs) was investigated by photo-dimerization. Uniform NLC alignment by linearly polarized UV exposure at normal incidence on the PCEMA surfaces having a high density of cinnamoyl groups was observed. Also, excellent voltage-transmittance (V-T) curves for the photo-aligned TN-LCDs on the PCEMA surfaces was achieved. We find that the V-T and response time characteristics can be improved by increasing the density of cinnamoyl groups.     

Generation of pretilt angle in NLCs and EO characteristics of a photo-aligned TN-LCD with oblique non-polarized UV light irradiation on a polyimide surface

We have investigated the generation of pretilt angle for a nematic liquid crystal (NLC) alignment in cells with oblique non-polarized ultraviolet (UV) light irradiation on polyimide (PI) surfaces. It was found that monodomain alignment of the NLC is obtained with an incident angle of 70 degrees and 75 degrees on the PI surface. It is considered that this alignment may be attributed to the anisotropic dispersion force due to photo-depolymerization of polymer on PI surfaces. Also, the generated NLC pretilt angles are all about 3 degrees at an incident angle of 70 degrees and 75 degrees for 1 h irradiation. Next, we observed that the voltage-transmittance characteristics for a photo-aligned twisted nematic (TN) LCD with an incident angle of 80 degrees on a PI surface were excellent. Also, we measured that the voltage-holding-ratio (VHR) of a photo-aligned TN-LCD is about 94%; it is almost same as obtained for rubbing-aligned TN-LCDs. Finally, the slow response time of photo-aligned TN-LCDs is attributable to their weak anchoring strength.     

Electro-optical characteristics of photo-aligned TN-LCD on PM4Ch surface

In this study, a photo-alignment material PM4Ch, poly(4-methacryloyloxychalcone), was synthesized. The electro-optical characteristics of a photo-aligned twisted nematic liquid crystal display (TN-LCD), with linearly polarized UV exposure at normal direction on a PM4Ch surface, were investigated. The NLC alignment was uniform. Excellent voltage-transmittance characteristics were obtained; a fast response time was also achieved. Reduction of d.c. voltage decreases with increasing UV exposure time.     

Electro-optical characteristics of photo-aligned TN-LCD on PM4Ch surface

In this study, a photo-alignment material PM4Ch, poly(4-methacryloyloxychalcone), was synthesized. The electro-optical characteristics of a photo-aligned twisted nematic liquid crystal display (TN-LCD), with linearly polarized UV exposure at normal direction on a PM4Ch surface, were investigated. The NLC alignment was uniform. Excellent voltage-transmittance characteristics were obtained; a fast response time was also achieved. Reduction of d.c. voltage decreases with increasing UV exposure time.     

Response time mechanism for a photo-aligned vertical-alignment liquid crystal display on a homeotropic alignment layer

The electro-optical characteristics of the photo-aligned vertical-alignment liquid crystal display (VA-LCD) with a non-polarized UV exposure of 45° on homeotropic polyimide (PI) surface was investigated. The domain size of the photo-aligned VA-LCD increases proportionately with the UV exposure time. The LC alignment of the photo-aligned VA-LCD is attributed to photo-dissociation of the polymer by UV exposure on the homeotropic PI surface. Good voltage-transmittance characteristics of the photo-aligned VA-LCD without negative compensation film was measured. The response time of the photo-aligned VA-LCD was slow compared with a rubbing-aligned VA-LCD; this is considered to be due to the alignment of LC molecules.     

Response time mechanism for a photo-aligned vertical-alignment liquid crystal display on a homeotropic alignment layer

The electro-optical characteristics of the photo-aligned vertical-alignment liquid crystal display (VA-LCD) with a non-polarized UV exposure of 45° on homeotropic polyimide (PI) surface was investigated. The domain size of the photo-aligned VA-LCD increases proportionately with the UV exposure time. The LC alignment of the photo-aligned VA-LCD is attributed to photo-dissociation of the polymer by UV exposure on the homeotropic PI surface. Good voltage-transmittance characteristics of the photo-aligned VA-LCD without negative compensation film was measured. The response time of the photo-aligned VA-LCD was slow compared with a rubbing-aligned VA-LCD; this is considered to be due to the alignment of LC molecules.     

Encapsulation of nanomaterials using an intermediary layer cross‐linkable ABC triblock copolymer

For the preparation of core‐shell nanoparticles containing functional nanomaterials, a photo‐cross‐linkable amphiphilic ABC triblock copolymer, poly(ethylene glycol)‐b‐poly(2‐cinnamoyloxyethyl methacrylate)‐b‐poly(methyl methacrylate) (PEG‐PCEMA‐PMMA), was synthesized. This triblock copolymer was then used to encapsulate Au nanoparticles or pyrene. The triblock copolymer of PEG‐b‐poly(2‐hydroxyethyl methacrylate)‐b‐PMMA (PEG‐PHEMA‐PMMA) (M_n = 15,800 g/mol, M_w/M_n = 1.58) was first synthesized by activators generated by electron transfer atom transfer radical polymerization. Its middle block was then functionalized with cinnamoyl chloride. The degrees of polymerization of the PEG, PHEMA, and PMMA blocks were 45, 13, and 98, respectively. PMMA‐tethered Au nanoparticles (with an average diameter of 3.0 nm) or pyrene was successfully encapsulated within the PEG‐PCEMA‐PMMA micelles. The intermediary layers of the micelles were then cross‐linked by UV irradiation. The spherical structures of the PEG‐PCEMA‐PMMA micelles containing Au nanoparticles or pyrene were not changed by the photo‐cross‐linking process and they showed excellent colloidal stability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4963–4970, 2009     

Synthesis,photo-reaction and photo-induced liquid crystal alignment of soluble polyimide with pendant cinnamate group

In this paper, the synthesis, photo-reaction and photo-induced liquid crystal alignment of a polyimide with a pendant cinnamate group are reported. The polyimide was synthesized by the thermal imidization of the polyamic acid derived from 4,4'-(hexafluoro-isopropylidene)diphthalic anhydride and hydroxydiaminopropane, followed by the attachment of the cinnamate group to the main chain polyimide. The surface of thin layers of the polyimide was found to be preferentially occupied by the pendant cinnamate groups, and liquid crystal alignment on the polyimide thin film exposed to polarized UV was independent of the cinnamate content. The thermal stability of the photo-induced liquid crystal alignment was enhanced with decrease in the cinnamate content. This could be attributed to the strong interchain interaction of the polyimide chains which prevents thermal randomization of the photo-product of the pendant cinnamates. The dependences of the photo-reaction temperature and the annealing temperature of the alignment layer on the azimuthal anchoring energy of the photo-aligned liquid crystal suggest that the local stress developed during the UV irradiation profoundly influences the thermal stability of the liquid crystal alignment.     

Diblock copolymer nanostructures

Polystyrene-block-poly(2-cinnamoylethyl methacrylate) (PS-b-PCEMA) and poly(acrylic acid)-block-poly(2-cinnamoylethyl methacrylate) (PAA-b-PCEMA) were synthesized. These polymers formed micelles with PCEMA as the core in solvents poor for the PCEMA block but good for the other blocks. When the PS block was much longer than the PCEMA block, star micelles were prepared. The PCEMA cores of these micelles were then photo-crosslinked to yield PS star polymers. Nanospheres of PCEMA were obtained by photolyzing crew-cut micelles of PAA-b-PCEMA, in which the water-soluble PAA block was much shorter than the water-insoluble PCEMA block. PS-b-PCEMA self-assembled at silica and their THF/cyclopentane micellar solution interfaces to form diblock monolayers called polymer brushes, in which the insoluble PCEMA block spread like a melt on the silica surface and the chains of the soluble PS block stretched into the solution phase like bristles of a brush. By tuning the relative composition, PCEMA in bulk formed cylindrical micro-domains dispersed in the continuous PS matrix. Irradiation of the PS-b-PCEMA brushes enabled our preparation of crosslinked PS-b-PCEMA monolayers. Nanofibers were prepared by dissolving in THF the irradiated PS-b-PCEMA films with crosslinked cylindrical PCEMA micro-domains.     

Synthesis, photo-reaction and photo-induced liquid crystal alignment of soluble polyimide with pendant cinnamate group

In this paper, the synthesis, photo-reaction and photo-induced liquid crystal alignment of a polyimide with a pendant cinnamate group are reported. The polyimide was synthesized by the thermal imidization of the polyamic acid derived from 4,4'-(hexafluoro-isopropylidene)diphthalic anhydride and hydroxydiaminopropane, followed by the attachment of the cinnamate group to the main chain polyimide. The surface of thin layers of the polyimide was found to be preferentially occupied by the pendant cinnamate groups, and liquid crystal alignment on the polyimide thin film exposed to polarized UV was independent of the cinnamate content. The thermal stability of the photo-induced liquid crystal alignment was enhanced with decrease in the cinnamate content. This could be attributed to the strong interchain interaction of the polyimide chains which prevents thermal randomization of the photo-product of the pendant cinnamates. The dependences of the photo-reaction temperature and the annealing temperature of the alignment layer on the azimuthal anchoring energy of the photo-aligned liquid crystal suggest that the local stress developed during the UV irradiation profoundly influences the thermal stability of the liquid crystal alignment.     

Block Copolymer Nanotubes

Rigid cylindrical micelles are made from polyisoprene-block-poly(2-cinnamoylethyl methacrylate)-block-poly(tert-butyl acrylate). The PI-PCEMA-PtBA polymer assembles to micelles with PI as the core, PCEMA as the shell, and PtBA as the corona. The cylindrical structure is fixed by photocrosslinking the PCEMA shell, and PCEMA-PtBA nanotubes are obtained by degrading the PI core with ozone (see scheme).     

Synthesis,self‐assembly,and formation of photo‐crosslinking‐stabilized fluorescent micelles covalently containing zinc(II)‐bis(8‐hydroxyquinoline) for ABC triblock copolymer bearing cinnamoyl and 8‐hydroxyquinoline side groups

Triblock copolymers (MPEG‐b‐PCEMA‐b‐PHQHEMA) bearing cinnamoyl and 8‐hydroxyquinoline side groups with different block length are synthesized by a two‐step reversible addition fragmentation chain transfer polymerization of cinnamoyl ethyl methacrylate (CEMA) and 2‐((8‐hydroxyquinolin‐5‐yl)methoxy)ethyl methacrylate (HQHEMA), respectively. The self‐assembly of MPEG‐b‐PCEMA‐b‐PHQHEMA in mixture of THF and ethanol is investigated by varying the ratio of THF and ethanol. Spheric micelles with diameter of 63.7 nm and polydispersity of 0.128 are obtained for MPEG₁₁₃‐b‐PCEMA₁₅‐b‐PHQHEMA₁₇ in THF/ethanol with a volume ratio (v/v) of 5/5. The PCEMA inner shell of the resulted micelles is photo‐crosslinked under UV radiation to give stabilized micelles. The complex reaction of the stabilized micelles with Zn(II) is investigated under different conditions to give zinc(II)‐bis(8‐hydroxyquinoline)(Znq₂)‐containing micelles. When the complex reaction is carried out in THF/ethanol (v/v = 5/5) or THF/toluene (v/v = 6/4) with zinc acetate, fluorescent Znq₂‐containing micelles are obtained without obvious change in diameters and morphologies. The fluorescent micelles exhibit green emission with λ_max at 520 nm. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1056–1064     

Thermosensitive Polymer Nanocontainers Prepared by Self-Assembly of Block Copolymers

In recent years, considerable effort has been devoted to the preparation of polymer nanocontainers because of their unique advantages. Compared to polymer microspheres or micelles,polymer nanocontainers are hollow-sphere structures and can encapsulate large quantities of guest molecules or large-sized guests within the "empty" core domain. Compared to polymer vesicles,polymer nanocontainers have enough mechanical stability to prevent them from structure changes due to covalent or ionic interactions responsible for their formation. Therefore, polymer nanocontainers have many potential applications such as confined reaction vesicles, drug carriers,protective shells for cells or enzymes, artificial cells and so on. However, most of polymer nanocontainers reported by now, load and release guest molecules from their interior only through diffuse mechanism. It is rather difficult to control intelligently the process based on demands. In order to solve this problem, one promising strategy is to design intelligent polymer nanocontainers.They can undergo reversible structural transitions from a closed to an open state with the help of external stimuli.In this paper, we report on our preliminary study of the thermosensitive polymer nanocontainers formed by self-assembly of the block copolymers PCEMA-b-PNIPAM and sequent photo-crosslinking of PCEMA shells.Block copolymers PCEMA-b-PNIPAM were prepared by reacting PHEMA-b-PNIPAM with excess cinnamoyl chloride in pyridine at room temperature, where PHEMA-b-PNIPAM was prepared by reacting succinimidyl ester of PHEMA-COOH with PNIPAAm-NH2, similar to the method of the literature. The block copolymers were characterized by FTIR and 1H-NMR and GPC.To obtain polymer vesicles, deionized water, as a precipitant, was added at a rate of 0.3wt%/10s with vigorous stirring to the PCEMA-b-PNIPAM solution in THE After the formation of polymer vesicles, more water was added until the water content reached ca.50wt%. The hollow structure of the polymer vesicles was clearly observed by TEM. Polymer nanocontainers with diameter range from tens of nanometers to thousands of nanometers can be obtained by changing formation condition. In order to obtain polymer nanocontainers with enough mechanical stability, the above polymer vesicles were crosslinked using UV light with a wavelength of 254 nm. The conversion of CEMA with irradiation time was monitored by measuring the decrease in absorbance at 274 nm,where converted PCEMA does not absorb. The CEMA conversion can be controlled from 0% to 50% by prolonging irradiation time. TEM images confirm that the morphology of the polymer nanocontainers is kept after irradiation.The thermosensitive property of the polymer nanocontainers in water was investigated using a Vis-UV spectrophotometer. The phase transition of the polymer nanocontainers takes place at about 40℃, and the structural reversibility in heating and cooling circle can keep well at least three times.     

Functional polymethacrylates as bacteriostatic polymers

Two copolymers, P(PCEMA-co-MMA) and P(t-BMA-block-PCEMA), were prepared via ATRP using 2-(phenoxycarbonyloxy)ethyl methacrylate (PCEMA) as reactive monomer and methyl methacrylate (MMA) or tert-butyl methacrylate (t-BMA) as co-monomers. Alternatively phenoxycarbonyloxy decorated polymethacrylates were obtained via polymer analogous reaction: P(HEMA) was reacted with phenyl chloroformate to yield P(PCEMA). The highly reactive phenoxycarbonyloxy groups were used for polymer analogous reactions with nucleophiles to obtain polymers with ionic/hydrophilic and hydrophobic side groups. Different amines with long alkyl chains or tertiary amine groups were reacted with phenoxycarbonyloxy decorated polymers and subsequently reacted with methyl iodide to obtain amphipathic polymers with bacteriostatic properties.     

从三嵌段共聚物制备纳米空心纤维的研究

近年来 ,利用分子自组装技术制备纳米材料已引起人们越来越多的兴趣[1] ,而从三嵌段共聚物在选择性溶剂中形成可分散的纳米颗粒并通过化学改性的方法使其具有某种功能或用作功能化的载体更具有实际意义 [2 ] .本文从由阴离子聚合得到的窄分布三嵌段共聚物出发 ,成功地制备了纳米空心纤维 ,将有可能用于制备纳米导线及模板聚合等方面 .1　实验部分1 .1　样品制备　采用阴离子聚合方法制备三嵌段共聚物 ,用凝胶色谱测定分子量分布宽度 ,光散射测定重均分子量 ,NMR测定其化学组成比 .将共聚物的甲苯浓溶液 (质量分数 30 % )倒入培养皿中并密…     

Photochemical stability of collagen/poly(ethylene oxide) blends

The photochemical stability of the blends of collagen and poly(ethylene oxide) PEO has been studied by Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy and viscosimetry. Surface properties before and after UV irradiation were observed using an optical microscope.Collagen and PEO were immiscible in diluted solution and only small interactions between the two components in the solid state were observed. New materials based on the blending of collagen and PEO that we obtained have a different photochemical stability than those of single components. In general, collagen/PEO blends are less stable under UV irradiation than pure collagen. The influence of PEO on the photochemical stability of collagen depends on the concentration of this polymer in the blend. Microscopic photographs show that the surface characteristics of thin films of collagen/PEO blends are not drastically altered after UV irradiation.