一种带肉桂酸酯基的聚酰亚胺液晶光定向材料研究

利用双酚A二胺单体(BISDA)与4,4-′(六氟异丙基)-双邻苯二甲酸酐(6FDA)的缩聚反应,制备了含有侧羟基的先驱聚合物PI-OH.通过PI-OH与肉桂酰氯的官能化反应,得到接有肉桂酸酯感光侧基的双酚A型聚酰亚胺PI-CI.用红外光谱(FTIR)、氢核磁共振(1H-NMR)分析、热分析(DSC)等方法表征了上述聚合物的结构和热性能.利用紫外-可见光谱(UV-Vis)对PI-CI的感光性能进行了研究.在线偏振紫外光辐照下,上述聚合物膜表现出二色向性.二向色性的强弱随光照能量的变化存在最大值.经线性偏振紫外光(LPUV)辐射后的PI-CI薄膜能诱导液晶盒中液晶分子发生均匀的定向沿面排列.上述实验表明,该聚酰亚胺是一类具有优良性能的潜在液晶光定向材料.     

NEW BLUE CROSSLINKABLE POLYMERS FOR ORGANIC LIGHT EMITTING DEVICES

Here, we report on new blue electroluminescence (EL) crosslinkable polymers containing fluorene/phenylene alternating repeating units. Additionally, they contain polymerizable oxetane groups attached through flexible hexyloxy chains to phenylene units of the polymer backbone. The copolymers were synthesized via Pd-catalyzed Suzuki coupling reactions. The copolymers obtained were found to be soluble and easily processable from common organic solvents such as chloroform or toluene and have been characterized by ¹H and ¹³C NMR spectroscopy, FT-IR spectroscopy and elemental analysis. The degree of polymerization has been determined by gel permeation chromatography (GPC). The thermal properties of the copolymers have been characterized by differential scanning calorimetry (DSC). The optical properties of the polymers were investigated in solution by UV/VIS spectroscopy. The polymers were photo-crosslinked in spin-coated thin films to yield insoluble networks.     

Triplet‐sensitized irradiation of a main‐chain liquid crystalline poly(aryl cinnamate) in three different phases

Visible light irradiation of thin films of a main‐chain liquid crystalline poly(aryl cinnamate) using ketocoumarins as triplet sensitizers leads to photochemical crosslinking and UV‐vis and FTIR spectroscopic changes associated with saturation of the cinnamate double bond, most likely by 2 + 2 photocycloaddition. The triplet sensitizers are themselves photolabile and are lost by photochemical reactions during the sensitization process. A new ketocoumarin sensitizer with decyloxy substituents and a reduced tendency to phase separate from the polymer is reported. A simple calculation of the sensitization stoichiometry shows that a single molecule of this ketocoumarin sensitizes the destruction of approximately 90 cinnamate chromophores in the “as cast” films below T_g and about 300 chromophores in the more‐ordered glassy nematic films and in “as cast” films of poly(vinyl cinnamate). Triplet sensitization of fluid nematic films leads, upon initial irradiation, to UV‐vis hyperchromism that is attributed to disruption of chromophore aggregation and, possibly, to disruption of the nematic mesophase as photoproducts begin to form. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 134–144, 2001     

Effects of monomer structure on the morphology of polymer networks and the electro-optical properties of polymer-dispersed liquid crystal films

Polymer-dispersed liquid crystal (PDLC) films were prepared by photochemical polymerisation with a series of (meth)acrylate monomers. The effects of monomer structure on the morphology of polymer networks in the PDLC films were studied. The acrylate monomers without sidegroup chain formed uniform polymer networks. The methacrylate monomers with methyl as their sidegroup chains formed lace-like networks. The size of the LC droplets increased with increasing the length of the flexible chain of both methacrylate and acrylate monomers. Meanwhile, the effects of the morphology of the polymer network on the electro-optical properties of PDLC films were also investigated.     

Cinnamates. III. The light sensitive polymers: Cinnamates with internal charge-transfer spectroscopic properties

In this paper, we outline the photochemical and spectroscopic properties of a new light-sensitive polymer obtained as a result of polystyrene modification by attachment of a pendant 4-dimethylamino-cinnamate ester group. This specific cinnamate displays typical charge-transfer character in the absorption and emission spectra. The photochemical and photophysical properties of photopolymer are compared with the monomeric model photochemistry and photophysics.     

Nanowear studies in chemically heterogeneous responsive polymeric brushes by surface force microscopy

In this study, we present nanowear studies using surface force microscopy (SFM), on nanoscopic thin films of reversibly switchable binary polymer brushes [polystyrene (PS) + poly(2-vinylpyridine) (P2VP)] and respective monobrushes [polystyrene and poly(2-vinylpyridine)] synthesized via “grafting to” method. The aim was to tune the wear in nanothin polymer brush surfaces. Therefore, the effect of conformational switching of PS + P2VP brush on treatment with selective solvents for PS and P2VP chains on the wear process was investigated. Wear process on thick spin-coated films of PS and P2VP was also investigated for comparison. Nanowear experiments were performed using SFM tip by repeating scans over the surface to follow the wear process closely. The wear process on different surfaces was explained on the basis of molecular entanglement as well as adhesion and friction on the sample surface. For spin-coated PS film as well as PS and PS + P2VP brush surfaces (treated with toluene) with molecular entanglements at surface, wear mechanism involved formation of ripples. However, in case of spin-coated P2VP films as well as P2VP and PS + P2VP brush surfaces (treated with ethanol) with no molecular entanglements at surface, wear occurred via removal of polymer chains and their accumulation at the rim. For PS + P2VP surface treated with acidic water, wear mechanism was complex and inhomogeneous ripple formation was followed by formation of heaps of polymeric material in the center of scanned area. The extent of wear as measured either by root mean square roughness of the surface or spacing between the ripples, increased with the number of scans for all the surfaces. Our study shows that wear mode of polymer brush surfaces is different for different polymers and can be controlled/tuned by the use of binary polymer brushes.     

Photobactericidal films from porphyrins grafted to alkylated cellulose - synthesis and bactericidal properties

Two series of porphyrinic cellulose laurate esters plastic films, where the photosensitizers are covalently linked to the cellulosic polymer have been synthesised by using a “one-pot, two-step” esterification reaction. The photosensitizers were first covalently bounded to the cellulosic polymer using either 4- or 11-carbon spacer arms. The porphyrinic plastic films were then obtained by a second esterification with lauric acid. The reaction was studied according to reaction time, temperature, lauric acid amount, pyridine playing the role proton trapping base. Para-toluenesulfonylchloride has been proved to be a powerful activating agent for this reaction. The drawback of the steric hindrance of the porphyrinic macrocycle towards cellulosic hydroxyl groups has been overcome by increasing the number of carbon of spacer arms from 4- to 11-carbons. The photobactericidal activity of these materials was evaluated against Gram positive and Gram negative strains bacteria. First results show that these new plastic films display photobactericidal activity for porphyrin grafting percentage higher than 0.16, whereas the non-porphyrinic control allowed full growth of bacteria. These materials could be an alternative in order to overcome the growing bacterial multiresistance to classical antibiotics.     

Surface modification of HDPE, PP, and PET films with KMnO4/HCl solutions

Surface modification of high-density-polyethylene (HDPE), polypropylene (PP), and poly(ethylene terephthalate) (PET) films was promoted by potassium permanganate solutions in HCl acidic medium using eight conditions by varying time, temperature, and oxidative solution concentration. This oxidation system introduced different amounts of carbonyl-carboxyl and hydroxyl groups onto the polymer surfaces. Drop water contact angle, FTIR, TGA, and SEM were used to assess oxidation efficiency and the surface changes suffered by the polymer film. The hydrophilicity of films obtained by contact angle was analyzed using a 2³ factorial design in Design-Expert^® program to obtain the main effects, the variance, and the interaction between the effects in action in the oxidation process.     

Photoresponsive polyamides containing pentamethylated norbornadiene moieties: Synthesis and photochemical properties under sunlight irradiation

Photoresponsive polyamides containing main‐chain pentamethylated norbornadiene (NBD) moieties are obtained in quantitative yields via the Yamazaki–Higashi reaction between a pentamethylated NBD dicarboxylic acid and a series of aromatic diamines. Chemical structures are confirmed by ¹H and ¹³C NMR and weight average molar masses measured by SEC are in the range of 21,500–28,600 g mol^?1 with chain dispersities close to 2. Physical properties are investigated by FTIR, differential scanning calorimetry (DSC), thermogravimetric analysis, and viscosimetry. All obtained polyamides are amorphous with glass transition temperatures ranging from 68 to 124 °C. They are soluble at room temperature in common organic solvents and exhibit good thermal stabilities with T_d10 values ranging from 175 to 276 °C. The photochemical isomerization of the NBD moiety into quadricyclane (QC) is studied by UV/vis spectroscopy after sunlight irradiation of polymer films. For all polyamides, a first‐order kinetic rate is observed for the conversion of NBD to QC. The thermal release of the stored energy associated to the reverse transformation of QC groups into NBD ones is about 90–95 kJ mol^?1 as measured by DSC of the irradiated polymer films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4650–4656     

A new method of growing crystalline networks in polymer matrices by simultaneous CT complex formation and in situ crystallization

A new method of preparing conductive polymer composites by growing crystalline networks of conductive additives in polymer matrices (reticulate doping) is described. The method consists of treating the polymer containing molecularly dispersed donor additive with acceptor/solvent vapors. In the swollen polymer layer simultaneously CT complex formation and crystallization takes place which for proper conditions leads to the formation of a network of the CT complex crystallites, making the film surface-conducting. The preparation and properties of surface conductive films using several electron donors and an iodine acceptor are described. The films obtained show surface resistivities of 10⁴–10⁶ ohm and are generally stable under ambient conditions.     

Stimuli-responsive properties of N-isopropylacrylamide-based ultrathin hydrogel films prepared by photo-cross-linking

To develop stimuli-responsive ultrathin polymer films on a solid substrate, a novel photo-cross-linkable polymer with both temperature- and pH-responsive properties was prepared. The photoreactive 4-aminobenzophenone (BP) was introduced onto the side groups of poly(N-isopropylaclylamide-co-2-carboxyisopropylaclylamide) [poly(NIPAAm-co-CIPAAm)]. This copolymer was designed for highly random sequences of comonomers. After the formation of spin-coated polymer films on a solid substrate, UV-light irradiation started the cross-linking reaction. The spin-coating processes and stability of the polymer films were quantitatively monitored by a quartz crystal microbalance (QCM), and the thickness was estimated using an atomic force microscope (AFM). These measurements confirmed the formation of a very plain polymer film, and the film thickness was precisely controlled by the concentration of the polymer solution used for spin coating. Moreover, the obtained films showed a high stability due to the cross-liking reaction and UV irradiation. Cyclic voltammetry using potassium ferricyanide revealed that the ions could permeate the photo-cross-linked ultrathin polymer films. The permeability of the ultrathin hydrogel films was dramatically changed by varying the pH and temperature of the aqueous media. These observations suggest that the preparation of isopropylacrylamide-based stimuli-responsive ultrathin hydrogel films is possible.     

A novel liquid crystals photoalignment layer-by-layer self-assembled film fabricated with long side-chain cinnamate polyelectrolyte

A novel photoalignment film for liquid crystals (LC) was prepared based on layer-by-layer self-assembly of photosensitive long side-chain cinnamate polyelectrolyte. A series of self-assembled films with different methylene spacer groups was prepared and used as alignment film. The film became anisotropic, and could induce uniform alignment of LC after irradiation by linearly polarised ultraviolet light (LPUVL). The effects of spacer chain lengths of the cinnamoyl polycations on the structure and photoalignment properties of the self-assembled film were studied. The polycation films with longer spacer chain obtained a larger dichroic ratio after LPUVL irradiation. The contrast ratio (T _max/T _min) of the LC cell increased with spacer chain length increase. However, it was found that the thermal stability of PSS/PACPYn films decreased with increasing chain length of polycation.     

Iridium metal–polymer complexes based on bipyridyl ligands

Novel polymer macroligands—copolyamides containing different quantity of bipyridyl groups—were obtained from 4,4′-diamino-2,2′-bipyridine, 4,4′-diaminodiphenyl ether and terephthaloyl-bis(3-methoxy-4-hydroxybenzoic) acid dichloroanhydride by low-temperature polycondensation. Metal–polymer complexes with different content of Ir(ppy)2 were obtained by the interaction between polymer ligand and [Ir(ppy)2Cl]₂ (ppy–2-phenylpyridine). The properties of films and coatings based on these materials were studied.     

Chirooptical and photooptical properties of a novel side-chain azobenzene-containing LC polymer

Abstract  A novel chiral–photochromic side-chain polyacrylate with azobenzene fragments in the side groups has been synthesised. It was shown that the polymer forms a smectic phase and a cholesteric supramolecular helical structure with selective light reflection in IR spectral range. Thin spin-coated films of the polymer were prepared and their photooptical and chirooptical properties were studied in detail. It was found that UV irradiation of the films led to E–Z isomerization of the azobenzene moieties with high conversion, which is dependent on thermal prehistory of the films. Subsequent action of visible light results in partial recovery of the E-isomer content, whereas annealing leads to the full back conversion. Circular dichroism (CD) measurements revealed formation of the helical supramolecular structure even in the initial spin-coated polymer films. The E–Z isomerization induces complete disruption of helical order in non-annealed films of the polymer, whereas in the smectic phase of the annealed film only a significant decrease in CD values was found. In addition, the photoorientation phenomena induced by polarized light were studied. It was shown that polarized light induces linear dichroism in the films provided by azobenzene group orientation and the dichroism is stable at room temperature for a prolonged time. These combined chirooptical and photooptical features of this novel polymer enable one to consider this multifunctional compound as a promising material for photonics and for optical applications. Graphical abstract  

Designed synthesis and chiroptical properties of regioregular poly(p-phenyleneethynylene-alter-m-phenyleneethynylene) bearing (−)-trans-myrtanoxyl side groups

Two regioregular poly(p-phenyleneethynylene-alter-m-phenyleneethynylene)s bearing (−)-trans-myrtanoxyl side groups with different substitution patterns were designed and synthesized, e.g. Myr-PMPE-1 and Myr-PMPE-2. In Myr-PMPE-1, the side chiral groups are distributed uniformly along the backbone. In Myr-PMPE-2, the distribution of the side chiral groups is alternatively crowded and loose. Both of these two polymers show no CD signal in solutions because of their good solubility. The investigations of chiroptical properties of these two polymers were carried out in the form of spin-coated films. The films were annealed above the glass temperature of the corresponding polymer, and the effects of annealing temperature and time on the properties of the films were investigated by UV-Vis absorption, fluorescence and circular dichroism spectra. The results show that annealing treatment had no significant effect on the properties of Myr-PMPE-1, including UV-Vis absorption, fluorescence and optical activity. The maximum absolute value of dissymmetry factor (|g _max|) was 1.62 × 10⁻⁴. On the other hand, annealing treatment significantly affected the properties of Myr-PMPE-2. Without annealing or being annealed below 100°C, Myr-PMPE-2 films show almost no Cotton effect. In contrast, when annealed above 120°C, the absorption and emission of Myr-PMPE-2 films slightly red shifted with increasing annealing temperature and annealing time. Most importantly, the intensity of CD signals increased significantly and the optical activity of Myr-PMPE-2 films markedly increased. After annealing at 140°C for 4 h, the |g _max| of Myr-PMPE-2 films was increased up to 3.07 × 10⁻³, about one order of magnitude higher than that of Myr-PMPE-1 films. __________ Translated from Acta Polymeric Sinica, 2008, 3 (in Chinese)     

Monitoring of the Sol-Gel Synthesis of Organic-inorganic Hybrids by FTIR Transmission,FTIR/ATR,NIR and Raman Spectroscopy

Summary: The sol-gel synthesis of organic-inorganic hybrids based on triethoxysilane- terminated poly(ethylene oxide) and tetraethylorthosilicate was monitored in-situ using three spectroscopic methods (FTIR/ATR, Raman, NIR). These spectroscopic methods allow in-situ monitoring of the evolution of hybrid materials starting from the modification of the polymer and the early steps of hydrolysis up to the network formation. By application of ²⁹Si solid-state NMR spectroscopy the assignment and quantification of the Raman bands to different end groups and different cross-linking states was made. The sol-gel reaction was also followed by in-line NIR spectroscopy. A multivariate data analysis was accomplished to obtain a conversion-time curve. Furthermore, we investigated spin-coated films on wafers using FTIR transmission spectroscopy.     

Sulfur-containing polymers. II. Preparation and properties of polycarbamoylsulfenamides

Polycarbamoylsulfenamides have been prepared by interfacial and solution polycondensation of chlorocarbonylsulfenyl chloride with diamines. In preparing the polycarbamoylsulfenamides, the following types of diamines were used: primary aliphatic diamines, a mixed primary-secondary aliphatic diamine, primary aromatic diamines, and secondary aromatic diamines. The properties of the resulting polymers depended primarily on the kind of diamines used. Transparent, tough films were obtained from the polymer based on N,N′-dimethyl-4,4′-diaminodiphenylmethane. The photochemical decomposition of the polymers has been studied.     

Interpenetrating polymer networks with stable second order nonlinear optical properties

Interpenetrating polymer networks (IPNs) based on polyurethane and polyacrylate-containing 4-(4'-nitrophenylazo) aniline chromophore groups were synthesized and characterized by infrared spectra, gel content and differential scanning calorimetry. Thin, transparent films of the IPNs were prepared by spin-coating, followed by thermal curing and corona poling. The poled IPN film shows very good optical properties and exhibits only one glass transition temperature. The second-order nonlinear optical (NLO) properties of the poled film were studied by visible light absorbance measurement according to one-dimensional rigid oriented gas model. The second-order nonlinear optical polarizability can reach 10^-7 e.s.u. The poled IPN film of defined composition showed a good temporal stability of NLO properties at 120°C for more than 160 hr.     

Photo-reorientation of azobenzene side groups of thermotropic ‘hairy rod’ polyglutamate in LB multilayers

A polyglutamate with photochromic azobenzene side groups combines thermotropic properties with the capability to form Langmuir-Blodgett (LB) multilayers. On irradiation with linearly polarised light the azobenzene side groups may be reoriented in spin-coated films and LB multilayers perpendicular to the electric field vector of the incident light. But the photochemically induced reorientation process depends strongly on the supramolecular order and on the irradiation conditions. Thus, the stable nematic-like order of the ‘hairy rod’ backbones restricts the photo-reorientation process of the azobenzene side groups within the LB multilayer, in contrast to the spin-coated film. In this case the degree of the photo-induced anisotropy depends on the primary orientational order of the multilayer, the molecular aggregation of the azobenzene moieties and on the conditions of light exposure. The photo-reorientation process becomes more efficient after weakening the intermolecular interactions by a suitable preparation of the films or by an intermediate photochemical decoupling of the supramolecular order caused by an ultraviolet irradiation step.     

Epoxy-based azo polymers with high chromophore density: Synthesis,characterization and photoinduced birefringence

Three epoxy-based azo polymers(PEP-AZ-Cl,PEP-AZ-CN and PEP-AZ-NT) with high chromophore density were synthesized by using post-polymerization azo-coupling reactions between epoxy-based precursor polymer(PEP-AN) and diazonium salts of 4-chloroaniline,4-aminobenzonitrile and 4-nitroaniline,respectively.The structures and properties of the azo polymers were characterized by using ~1H-NMR,FT-IR,UV-Vis and thermal analyses.The photoinduced birefringence of the azo polymers was studied by irradiating spin-coated films of the polymers with laser beam at three different wavelengths(488,532,and 589 nm).The results indicate that the photoinduced birefringence of the azo polymers is related with the electron-withdrawing group on azo chromophores and the excitation wavelength.The excitation wavelength that can cause the efficient responses is determined by the absorption band positions of the azo chromophores,which are mainly affected by the electron-withdrawing group on the chromophores.Therefore,the azo polymers containing chromophores with different electron-withdrawing groups show different responsive behavior to the irradiation light at different wavelengths.When irradiated with 488 nm light,PEP-AZ-Cl shows the shortest time to reach the saturated birefringence but with the lowest saturation birefringence level compared with the other two azo polymers.When irradiated with 532 nm light,PEP-AZ-CN shows the shortest time to reach the saturated birefringence.When irradiated with 532 and 589 nm light,PEP-AZ-NT shows the highest saturation birefringence level.