CHOLESTERIC LIQUID CRYSTALLINE CHARACTER ON THE SURFACE OF CHITOSAN/POLYACRYLIC ACID COMPOSITES*

The cholesteric liquid crystalline structure in chitosan/polyacrylic acid composite films was studied by surfacetechniques. A periodical lamellar-like structure was observed in the permanganic acid etched film sufface by both scanningelectron microscopy (SEM) and atomic force microscopy (AFM), instead of the thumb-print texture which can be detectedwith polarized optical microscopy. It is suggested that the periodical lamellar-like structure is induced by the etchingselectivity between cholesteric layers due to different molecular arrangement on the film surface. Four kinds of perpendiculardisclinations, i.e. χ→τ→λ~+, χ→λ+τ~+, χ→τ+τ~+ and χ→λ~- +λ~+, were found in the composite films from SEMobservations. The smallest periodicity of lamellar-like structure (equals to half pitch) is 20～40 nm measured with AFM.     

SYNTHESIS AND OPTICAL PROPERTIES OF POLY (THIENYLACETYLENES)*

3 -Ethynyl-4-(trimethylsilyl)thiophene (1a) and 3 -ethynyl-4-bromothiophene (1 b ) selectivelyundergo acetylene polymerizations in the presence of the MoCl_5- and WCl_6-Ph_3SiH catalysts to give soluble,high-molecular-weight poly(thienylacetylenes) (2) (M_w up to 602000) in high yields (up to 100%). Lighttransmission spectra of THF solutions of 2 continuously red-shift with increasing concentration. Theconcentratochromism shows a logarithmic concentration dependence; that is, the optical transitions of 2 arepredictably tunable by simply changing their concentrations.     

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.     

SYNTHESIS AND PROPERTIES OF TRANSPARENT THIODIGLYCOL DIMETHACRYLATE COPOLYMER RESINS

The title compound, thiodiglycol dimethacrylate (TDGDMA), was synthesized from thiodiglycol and methacryloyl chloride by phase transfer catalysis reaction, and its structure was confirmed by FTIR and 1H-NMR analyses. TDGDMA possesses good polymerizability to produce a homopolymer resin with excellent transparency (T%, 90), moderate refractivity (nd20, 1.55), lower dispersivity (Abbe‘s number, 50.6) and higher glass transition temperature (Tg, I19℃). Through copolymerization with styrene (St) or styrene-4,4‘-bismethacryloyloxydiphenylsulfone (BPSDMA), many properties of the copolymer such as refractive index, Abbe‘s number, strength, onset wavelength in the UV region and density were significantly modified. A copolymer resin with balanced properties between refractive index and dispersion was produced at the weight ratio of TDGDMA:St:BPSDMA (25:50:25), where nd20 and Abbe‘s number are 1.5815 and 36.5, respectively.     

EFFECTS OF CHAIN STRUCTURE OF POLYPYRROLONES ON THE ELECTRICAL PROPERTIES OF PYROLYZED POLYPYRROLONES

Three kinds of polypyrrolones (PMDA-DAB, PMDA-TADPE and DEDA-DAB) werepyrolyzed at high temperature in order to study the effect of the chain structure of polypyrro-lones on the electrical properties of the pyrolyzed polymers. Results show that the num-ber of fusing rings in the main chain of polymers has a little effect on the pyrolysis pro-cess, whereas, the ether bond in the main chain plays an important role during pyrolysis.Structure characterizations by elemental analyis, XPS spectra, X-ray diffraction and SEMimages indicate that because the ether bond is easy to break, it is difficult to form largearea planar network. This hampers the formation of the graphite-like structure in thepolypyrrolones containing ether bond even after being pyrolyzed at 1200℃.     

PREPARATION AND PROPERTIES OF ETHYL-CYANOETHYL CELLULOSE/POLYACRYLIC ACID COMPOSITE FILMS WITH REFLECTION COLORS*

Ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid (AA) becomes a cholesteric liquid crystalline solution withvivid colors when the (E-CE)C concentration is 42 wt%～52 wt%. (E-CE)C/polyacrylic acid (PAA) composites withcholesteric structure were prepared by polymerzing AA in (E-CE)C/AA liquid crystalline solutions. The layers of orderedpolymer chains in the cholesteric phase were inclined during polymerization and the degree of the inclination depended onthe polymerization temperature and the concentration of the solution before polymerization. The cholesteric structure in thecomposites could not be changed when temperature was lower than 100℃. Cross-linking of the PAA in compositesimproved their water-resistance. The cholesteric order of the composites without cross-linking was destroyed when theywhere immersed in water. The color derived from the selective reflection of the cholesteric phase of the cross-linkedcomposites turned from blue to red after the composites absorbed water. The color of the composites could be returned to theoriginal one when the absorbed water was removed from the swollen composites.     

VDF/TFE/PMVE三元共聚物的结构与性能研究

控制不同单体的起始组成合成了一系列偏氟乙烯 (VDF) 四氟乙烯 (TFE) 全氟甲基乙烯基醚 (PMVE)三元共聚物 ,通过1 9F NMR测定了这类三元共聚物的组成 ,结果与按竞聚率的计算结果吻合 .进一步分别用DSC和WAXD表征了玻璃化温度和结晶度 ,实验结果发现用这类三元共聚物制成的硫化胶的性能与其组成和微观结构密切相关     

SYNTHESIS AND CHARACTERIZATION OF SOME THERMOTROPIC LIQUID CRYSTALLINE POLYAMIDES

A series of novel mesogenic polyamides containing a flexible pendent side group wassynthesized by solution condensation polymerization. The new monomers, diacids and di-amines containing flexible elements of diferent lengths, were also synthesized and character-ized by ~1HNMR, mass spectroscopy and elemental analysis. The polymers were character-ized by viscosity measurements, differential scanning calorimetry (DSC), X-ray diffiactionand polarizing optical microscopy These studies revealed that polyamides containingflexible elements of a sufficient length exhibited thermotropic liquid crystalline(LC) pro-perties. The melting temperatures of this series of polymers were particularly sensitive tothe length of the flexible segment on the main chain and that of the flexible pendent esterside chain. Lyotropic LC behaviours were also observed in solution.     

SYNTHESIS AND PROPERTIES OF NEW MESOGEN-JACKETED LIQUID CRYSTALLINE POLYMERS*

Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, andmesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of thesepolymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Theirliquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. Theresults show that 1) a more flexible polymer main-chain is more favorable to the formation of a liquid crystal phase, while 2)a flexible spacer will decrease the "Jacket Effect" and the liquid crystallinity and 3) a subtle modification of the terminalgroups on the mesogenic unit may also have a significant influence on properties of the polymers.     

侧链胆甾液晶聚合物及弹性体的液晶性能研究

把胆甾液晶单体 4 烯丙氧基苯甲酸胆甾醇酯 (Mch)分别和向列液晶单体 4 烯丙氧基苯甲酰氧基 4′ 甲氧基苯 (Mn) ,向列液晶交联剂 2 叔丁基对苯二酚双 [4 (6 丙烯酰氧基己氧基 )苯甲酸酯 ](Mnc)接枝到聚硅氧烷链上 ,得到系列侧链液晶聚合物Pn 系列和液晶弹性体Pe 系列 .通过热分析、偏光显微分析和X 射线分析等手段分别研究了向列液晶单体和向列液晶交联剂对含同一胆甾液晶基元聚合物的影响 .结果表明 ,向列液晶单体的摩尔百分比在 80 %以下 ,液晶聚合物Pn 系列为胆甾型液晶 ,在研究的范围内 ,液晶弹性体Pe 系列也为胆甾型液晶 ,Pn 系列和Pe 系列都具有较宽的液晶相范围 ,热分解温度均在 2 80℃以上 .     

DIPOLE POLARIZATION RELAXATION AND MOLECULAR STRUCTURE OF MAIN-AND SIDE-CHAIN LIQUID-CRYSTALLINE POLYMERS

Molecular mobility in thermotropic polyesters and side-chain polymers with different struc-ture of mesogens and spacers has been studied by dielectrical method in dilutesolutions. The results made it possible to establish the multiplicity of dielectric relaxationtransitions which reflects the small- and large-scale types of molecular motion. It was shownthat dielectric relaxation processes occurring in accordance with local mechanism (relaxationtimes 10~(-9)--10~(-7)s. and the activation energy 10--50kJ/mol) are due to the mobility of kineticchain elements of different length within a monomer units. It was found that the dielectricrelaxation process connected with a large-scale form of molecular motion (relaxation times10~(-5)--10~(-6)s. and the activation energy 100kJ/mol) did not depend on the molecular massbut was infiuenced by factors changing the conformational state of the macromolecule. It isestablished tha the cooperative reorientation mobility of associated mesogenic fragments isthe source of the large-scale process.     

SYNTHESIS OF DIACETYLENE-CONTAINING COPOLYESTERS AND THEIR DFFECT ON ELECTRO-OPTICAL PROPERTIES OF LIQUID CRYSTALS*

Some diacetylene-containing copolyesters with different ratios of dipropargyl 1,10-decanate anddipropargyl terephthalate were synthesized. Properties of these copolymers were characterized by differentialscanning calorimetry and polarizing optical microscopy. The copolymer could be cross-linked easily by UVirradiation in a liquid crystal matrix without adding any photoinitiator. The preliminary studies showed thatthe diacetylene-containing polymer network can assist liquid crystal molecules to align with the externalelectric field, thus reducing the response time of display devices.     

INFLUENCE OF THE SOLVENT SWELLING ON MACROMOLECULAR CHOLESTERIC LIQUID CRYSTALLINE STRUCTURE*

Ethyl-cyanoethyl cellulose [(E-CE)C]/cross-linked polyacrylic acid [PAA] molecular compositeswith cholesteric order were prepared. It was found that the macromolecular cholesteric structure was changedwith the swelling of PAA in the composites. The selective reflection of the cholesteric phase shifted to thelonger wavelength and the X-ray diffraction angle shifted to the high angle direction during swelling, whichsuggested that the cholesteric pitch and the number of the layers of ordered (E-CE)C chains in the cholestericphase were increased.     

SYNTHESIS,CHARACTERIZATION AND OPTICAL PROPERTIES OF THE COPOLYMERS OF C_(60) AND 1-PHENYL-1-PROPYNE*

While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410×10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).     

ADDITIVE-INDUCED ENHANCEMENT OF OPTICAL CLARITY OF POLYACRYLAMIDE HYDROGEL

The aqueous polymerization of acrylamide and crosslinking with N,N-methylenebisacrylamide afforded hydrogelsdisplaying high levels of light scattering (poor optical clarity). Enhancement of the optical clarity within a polyacrylamide(PAm) hydrogel was accomplished through the implementation of "refractive index matching". Water-soluble additives wereutilised to better match the refractive index inhomogeneities throughout a given hydrogel. This resulted in lower lightscattering within the system and hence improved clarity. Amino acids, sugars, polymers, and other water-soluble additivessuch as glycerol were investigated by this methodology. Most additives investigaed displayed potential for effectivelyreducing the light scattering within a PAm hydrogel as a function of increased additive concentration. On increasing therefractive index of the water medium, the overall refractive index of a PAm hydrogel was also observed to increase. Thisprovided a quantitative means of determining the effectiveness of a given additive for improving the optical clarity within ahydrogel.     

EFFECT OF SEQUENCE STRUCTURE ON THE THERMOTROPIC LIQUID CRYSTALLINE PROPERTIES OF POLYESTERAMIDES BASED ON DIMETHYLBENZIDINE, BISPHENOL-A AND ρ-TEREPHTHALYL CHLORIDE*

A series of thermotropic liquid crystalline polyesteramides with differ-ent sequence structure based on dimethylbenzidine (DMBD), bisphenol-A(BPA) and p-terephthalyl chloride (TPC) was synthesized by changing the feeding order of monomers inlow temperature solution polycondensation system. By means of NMR and a computer pro-gram the sequence structure parameters were measured. The effect of sequence structureon liquid crystalline phase transition temperature of PEAs obtained was investigated.     

NONLINEAR OPTICAL PROPERTIES OF X-TYPE CHROMOPHORES AND THEIR DOPED FILMS

Two X-type chromophores, 2-[4-(4,5-di(4-nitrophenyl) imidazolyl) phenyl]-4,5-di(4-methoxyphenyl)-imidazole (DNPIPDMOPI), 2-[4-(4,5-di(4-nitrophenyl)-imidazolyl) phenyl]-4,5-di(4-aminophenyl)-imidazole (DNPIPDAPI), were synthesized and characterized. The results show that they possess good nonlinearity, considerable blue-shifted absorption (385 nm and 379 nm in THF) and high decomposition temperature (377℃ and 405℃). These mean that the X-type chromophores possess a rather good nonlinearity-transparency-thermal stability trade-off. The multi-step corona-poling technique at elevated temperature and in-situ SHG measurements were used to obtain and evaluate the poled films of these chromophores doped in PMMA. The largest SHG signals appeared at 110-120℃, which are 12.5 pm/V and 16.7 pm/V respectively. The dependence of poling induced orientation stability on temperature was measured by depoling experiments and the results indicate that the poling-induced orientation of the films is stable at about 100℃. Theoretic analyses imply that better orientation stability arises from the X-type structure of chromophore. The X-type chromophore has two crossed intramolecular CT, both βxxx and βxyy can contribute to the second-order susceptibility, and the ratio of the tensorial components (γ = βxyy/βxxx) is about 1/3, so the orientation decay of the films induced by rising temperature will provide a certain compensation for the contribution of βxyy of chromophores.     

LLDPE/纳米SiO_2复合材料的力学性能和光学性能研究

采用熔融共混方法制备了LLDPE 纳米SiO2 复合材料 ,并对该体系的力学性能和光学性能进行了系统研究 .结果表明 ,随着纳米SiO2 的加入 ,复合材料的弹性模量显著提高 ,冲击强度与拉伸强度呈峰形变化 ,且均在SiO2 含量为 3phr左右达到最大值 .加入少量的纳米SiO2 后 ,复合材料薄膜对长波红外线 (7～ 1 1 μm)的吸收能力较LLDPE膜有了显著提高 ,透光率略有下降但雾度提高 ,透光质量得到改善 .同时表明 ,纳米SiO2 的表面处理方法对膜的光学性能有显著影响