SYNTHESIS AND CHARACTERIZATION OF NOVEL BIPOLAR PPV-BASED COPOLYMER CONTAINING TRIAZOLE AND CARBAZOLE UNITS*

Two new blue light-emitting PPV-based conjugated copolymers containing both an electron-withdrawing unit(triazole-TAZ) and electron-rich moieties (carbazole-CAR and bicarbazole-BCAR were prepared by Wittig condensationpolymerization between the triazole diphosphonium salt and the corresponding dialdehyde monomers. Their structures andproperties were characterized by FT-IR, TGA, DSC, UV-Vis, PL spectroscopy and electrochemical measurements. Theresulting copolymers are soluble in common organic solvents and thermally stable with a T_g of 147℃ for TAZ-CAR-PPVand of 157℃ for TAZ-BCAR-PPV. The maximum photoluminescence wavelengths of TAZ-CAR-PPV and TAZ-BCAR-PPV film appear at 460 nm and 480 nm, respectively. Cyclic voltammetry measurement demonstrates that TAZ-BCAR-PPVhas good electrochemical reversibility, while TAZ-CAR-PPV exhibits the irreversible redox process. The triazole unit wasfound to be an effective π-conjugation interrupter and can play the rigid spacer role in determining the emission colour ofthe resulting copolymer.     

MORPHOLOGICAL STUDIES OF A THERMOTROPIC SIDE-CHAIN LIQUID CRYSTALLINE POLYMER DURING MESOPHASE TRANSITIONS*

The morphological features of a side-chain liquid crystalline polymer during the mesophasetransitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogensof three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture wasobserved in the transition temperature range. Similar to main-chain liquid crystalline polymers the transitionprocess of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at localplaces of the old phase matrix and a growth process of the new phase domains.     

TRANSITIONS AND MODRPHOLOGY OF MAIN-CHAIN LIQUID CRYSTALLINE POLYMERS WITH X-SHAPED MESOGENS

The transitions and morphology of a series of main-chain liquid crystalline polymer with X-shaped mesogens were studied by means of DSC,SALS and polarizing microscopy techniques. Aneven-odd effect was observed for samples with different size of the substituents on the mesogenends. The isotropization process was similar to that of main-chain polymers with rod-likemesogens. No crystallization was detected for specimens cooling down from their isotropic meltstate. However two of the samples may crystallize in cooling process directly from the liquidcrystalline state.     

SYNTHESES AND CHARACTERIZATION OF A NEW TYPE OF LIQUID CRYSTALLINE POLYESTERS

A new type of liquid crystalline polyesters with resorcin as one part of the mesogenic unitconnected together by polymethylene, or phenylene group, and lateral groups consisting of arigid azobenzene as another part of the mesogenic unit were synthesized by interfacialpolymerization of diacyl chlorides in 1, 2-dichloroethane and 2, 4-dihydroxy-4'-nitroazobenzen inaqueous alkaline solution. The polyester structures were confirmed by proton NMR and IRspectra. Their phase transition behavior and texture were studied by polarizing microscopy andDSC.     

MELT BLENDS OF POLY (BUTYLEN TEREPHTHALATE) AND A THERMOTROPIC LIQUID CRYSTALLINE POLYMER

With the help of differential scanning calorimetry, cone-plate and capillary rheometry andscanning electron microscopy, a research has been conducted on rheological behavior,crystallization and morphology of poly (butylene terephthalate) (PBT) blends containing athermotropic LCP. The blend has zero entrance pressure loss, although the LCP has rather largeone. The viscosity curve of the blend lies between those of the LCP and PBT. The crystallizationof PBT is not affected by the presence of the LCP together with no indication oftransesterification between the two ingredients. LCP spheres and ellipsoids with the size of 0. 5--1. 5 μm disperse in PBT matrix uniformly, which is related to the viscosity ratio of the twocomponents.     

SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC COPOLYESTERS AND COPOLY (ESTER-AMIDE)S CONTAINING OXYETHYLENE-ETHER AS THE SPACER

Flexible oxyethylene-ether was introduced into the aromatic copolyesters and copoly(es-ter-amide)s to reduce the melting point of resulting polymers. The melting point was greatlyreduced to 200℃ or even lower in some cases, and the molecular weight was satisfactorilyhigh as reflected by inherent viscosity. The polymers exhibited high thermal stability and goodmechanical properties as determined by TGA and mechanical tests. The copolyester showedbetter crystallinity and liquid crystallinity than corresponding copoly(ester-amide)s with simi-lar monomer composition as reflected by POM observation and WAXD study. The meltingpoints for both copolyesters and copoly (ester-amide)s showed great dependence on the p-acetoxybenzoic acid (PAB) content in monomer composition and reached the lowest valuewhen PAB was 29 mol%.     

SYNTHESIS AND CHARACTERIZATION OF SIDE CHAIN LIQUID CRYSTATALLINE POLYSILOXANES CONTAINING BENZYL ETHER LINKING UNITS

Side chain liquid crystalline polysiloxanes containing benzyl ether linkingunits were synthesized by the hydrosilylation of poly (methylhydrosiloxane) with a series of4-(4-alkoxybenzyloxy)-4'-allyloxybiphenyl monomers [4-(4-methoxybenzyloxy )-4'-allyloxy-biphenyl(M_1), 4-(4-ethoxybenzyloxy)-4'-allyloxybiphenyl (M_2), 4-(4-propoxybenzyloxy)-4'-allyloxybiphenyl (M_3), 4-(4-butoxybenzyloxy)-4'-allylox(M_4), 4-(4-pentoxy-benzyloxy)-4'-allyloxybiphenyl (M_5), 4-benzyloxy-4'-allyloxybiphenyl (M_6)]. The phasebehavior of monomeric and polymeric liquid crystals was characterized by differential scan-ning calorimetry and optical polarization microscopy where the groups are ranged frommethoxy to pentoxy Both the monomeric and polymeric liquid crystals exhibit 1iquidcrystal behaviors.     

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTAL POLYMERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS

Two series of new liquid crystailine polymers with T-shaped two-dimensional mesogenicunits were synthesized by low temperature solution polycondensations of 4-substituted N-2, 5- dihydroxybenzylidene aniline monomers with different diacyl dichlorides. The polymerswere found to be nematic and shown liquid crystailine behavior. The melting temperatureT_m and the clearing temperature T_i of the polymers change regularly with varying of themonomer structures.     

CHARACTERIZATION AND PROPERTIES OF URUSHIOL POLYMER CONTAINING BORON-NITROGEN COORDINATE BOND

Urushiol polymer containing B--N bond (PUBN) was synthesized with urushiol-boronpolymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC,DTA-TG and elemental analysis. The physico-mechanical and anticorrosive propertiesof the polymer were also investigated. The results show that the coating of PUBN canbe hardened in 2h at room temperaure and its film has excellent physico-mechanicalproperties and good anticorrosive properties.     

OPTICAL PHASE CONJUGATION RESPONSE OF PHOTOINDUCED POLYMER FILMS CONTAINING AZOBENZENE MOIETIES WITH CHIRAL GROUP

An optically active monomer containing azobenzene moieties with chiral group (s-2-methyl-butyl), 4-[2-(methacryloyloxy)ethyloxy]-4'-(s-2-methyl-1-butyloxycarbonyl) azobenzene(Ml) was synthesized. Polymer (PMl)possessing optical phase conjugated response was obtained by homopolymerzation of the optically active monomer (Ml)using free radical polymerization. The polymer was very soluble in common solvents and good optical quality films could beeasily fabricated by spin coating. The optical phase conjugated responses of the polymer PM1 were measured by degeneratefour-wave mixing (DFWM). In comparison with polymer containing no chiral group, it was found from the preliminarymeasurement of photoisomeric change that optical phase conjugated response of the PM1 in the long-range order hexagonalsymmetry microstructure could be easily controlled by choosing the appropriate polarization direction of the irradiatingbeams (514.5 nm) and the irradiating number, presumably due to the chiral group in the PM1 molecular structure. For thecase of the polymer investigated here, a chiral group side chain was introduced to increase optical phase conjugated responseintensity with different polarization directions of the irradiating beams, which aims originally at searching for a new photo-ative material.     

SYNTHESIS AND PROPERTIES OF A NEW AZOBENZENE SIDE-CHAIN POLYMER CONTAINING A TEMPO RADICAL

To allow anisotropies of optical properties in a magnetic field, nitroxide radical is introduced into the ortho-position of the phenylene ring in the side chain. A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPOradical was synthesized. The polymer has a good solubility in organic solvents. The ESR spectrum of the polymer indicatedthree absorption lines characteristic of TEMPO radical. The optical phase conjugated responses (I_4) of the polymer filmswere investigated by degenerate four-wave mixing (DFWM). The experimental results showed that optical phase conjugatedresponse of the TEMPO-PAZ could be easily controlled by choosing the appropriate direction of magnetic field presumablydue to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymer investigated here, the nitroxide radicalwas introduced to increase optical phase conjugated response intensity in a magnetic field, aiming originally at searching fora new photo-active organic magnetic multifunctional materials.     

INFLUENCE OF MOLECULAR WEIGHT OF CHITIN AND ITS THREE DERIVATIVES ON CRITICAL CONCENTRATION OF LYOTROPIC LIQUID CRYSTALLINE PHASE TRANSITION*

The critical concentration of lyotropic liquid crystalline phase transition for chitin derivatives was determinedusing a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution forchitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore itcan be used as an indicator of the chain rigidity.     

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.     

SYNTHESIS AND CHARACTERIZATION OF MAIN CHAIN AROMATIC LIQUID CRYSTAL COPOLYESTERS WITH X-SHAPED AND ROD-SHAPED MESOGENIC UNITS

A series of main chain liquid crystal aromatic copolyesters with X-shapedand rod-shaped mesogenic units were synthesized via solution condensation polymerizationsof 4, 4'-(α,ω-octanedioyloxy)-dibenzoyl dichlorides with 2,5-bis(p-octanoxy benzoyloxy)-hydroquinone and diphenol. All of the copolyesters showed thermotropic liquid crystallinebehaviors through observations using DSC, polarized microscopy and X-ray diffraction.The melting point (T_m) and the isotropization temperature (T) change regularly withvarying the content of diphenol unit in the copolymers.     

SYNTHESIS AND CHARACTERIZATION OF NEWLY DESIGNED POLY[DI(ALKYL) VINYLTEREPHTHALATE]S

A series of newly designed monomers of 2-vinylterephthalates (VT) were synthesized. The monomers contain onephenylene group connected with two alkyl groups (carbon number varying from 1 to 6) via ester linkage. Their chemicalstructures were confirmed by mass spectroscopy (MS), ~1-H-NMR, and elemental analysis (EA). The corresponding polymers,poly[di(alkyl) vinylterephthalate]s (PDAVTs), were obtained using convenional free redical polymerization. The polymerswere found to be able to develop inio liquid crystalline phase when the size of the alkyl group in the side-chain increases tobe larger than the ethyl group.     

PHOTOINDUCED BIREFRINGENCE AND NUMERICAL SOLUTION OF A NEW DYNAMIC MODEL IN AN AMORPHOUS COPOLYMER CONTAINING AZOBENZENE GROUPS*

Photoinduced birefringence is investigated in a new amorphous copolymer containing azobenzene groups. Thelevels of birefringence signal are found to depend on the polarization angle between the pump beam and the probe beam, andon the ellipticity of the pump beam. Both the growth and decay processes of the birefringence signal can be described byknown biexponential equations. The rate constants and the amplitudes associated with the growth process of thephotoinduced birefringence are observed to display a linear dependence with the pump beam intensity. A new dynamicmodel of the photoinduced birefringence is presented taking into account the contributions of both the trans and cis isomersof azobenzene groups and the local polymer segments. The numerical treatment of this model shows good agreement with theexperimental data in the whole writing-erasing processes of the photoinduced birefringence conducted in our polymersamples.     

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.     

SOME ASPECTS OF MORPHOLOGIES AND INTERFACES IN COPOLYMER/HOMOPOLYMER BLENDS

Based on a series of morphological studies of blends of homopolymer (Homo) and a variety of block and graft copolymers (Cop), the nature of phase separation, interface, emulsification and inner morphology of copolymer-dispersed phase etc. in the blends are discussed. In the cases of Cop AB/Homo A/Homo B systems, in which one homopolymer forms matrix, it is observed that the dispersed homopolymer phase is exclusively associated with Cop AB, i.e. no Homo A-Homo B interface exists. This phenomenon is believed to be caused by minimizing the interfacial energy of the systems. Meanwhile, preferential solubilization or anchoring of the like chains of copolymer into homopolymer matrix leads to stabilization of the dispersed phase in the matrix. In addition, regular variation of the inner morphology of the dispersed copolymer phase with the composition and molecular parameters of the component polymers is observed. When the two components have comparable proportions, alternating concentric shells are the most common feature which is associated with minimizing the interfacial energy in the Cop/Homo systems.     

COMPENSATION EFFECT OF POLYIMIDE THIN FILMS ON NORMALLY WHITE TWISTED NEMATIC LIQUID CRYSTAL DISPLAYS

The disadvantages of Normally White Twisted Nematic Liquid Crystal Display (NW-TN-LCD) were discussed. The reason that the negative birefringent polyimide thin filmswere used to compensate NW-TN-LCD to decrease off-axis leakage, improve contrast ratiosand enlarge viewing angles was explained in this paper. A certain polyimide thin film wastaken as an example to show compensation effect on NW-TN-LCD.     

SYNTHESIS AND PHASE BEHAVIOUR OF CHIRAL COMBINED MAIN/SIDE CHAIN LIQUID CRYSTALLINE COPOLYMERS

The synthesis and phase behaviour of chiral combined main/side chain liquid crystallinecopolymers containing pendant group constituted by chiral side group and trans-azobenzenemoiety with nitro end group are described. The formation of liquid crystalline polymorphism ofcopolymers is influenced by various contents of achiral side group.