SYNTHESIS AND PROPERTIES OF NEW MESOGEN-JACKETED LIQUID CRYSTALLINE POLYMERS

Some new mesogen-jacketed liquid crystalline polymers (MJLCP) with polymer backbones, spacers, and mesogenic units of different structures were synthesized by radical polymerization. The mesomorphic behavior of these polymers was examined using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Their liquid crystallinity is influenced by the variation of polymer backbone, spacer, mesogenic unit and its terminal groups. The results 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 terminal groups on the mesogenic unit may also have a significant influence on properties of the polymers.

Synthesis and Characterization of Sidechain Liquid Cryastalline Polysiloxanes Containting Either Cholesteryl or Cyanobiphenyl Mesogenic Groups

A series of side chain liquid crystalline polysiloxanes containing either cholesteryl or cyanobiphenyl mesogenic groups were synthesized by the hydrosilylation reaction of a polysiloxane containing Si H group with a vinyl terminated compound containing the mesogenic group. Their chemical structures were confirmed by IR, 1H NMR, and elemental analysis, Their phase behaviors were investigated by differential scanning calorimetry, optical polarizing microscope, and X ray diffraction techniques. The results show that all these polysiloxanes except PⅤ display smectic or nematic mesonorphism or both. The dependence of phase transition temperature on the rigidity of mesogenic unit. the length of spacer group, and the flexibility of Si(CH 3) 2O chain is also described.

STUDY ON LIQUID CRYSTAL POLYMERS WITH TWO-DIMENSIONAL MESOGENIC UNITS

A series of liquid crystalline polymers with two-dimensional mesogenic units were synthesized by solution polycondensation at low temperature. All the polymers were liquid crystalline. The melting temperature T;（except that with substituent of methoxy） and the clearing temperature T;of the polymers change regularly with varying of the length of the alkyl substituent groups.

"LIVING" FREE RADICAL SYNTHESIS OF NOVEL RODCOIL DIBLOCK COPOLYMERS WITH POLYSTYRENE AND MESOGEN-JACKETED LIQUID CRYSTAL POLYMER SEGMENTS

The synthesis of rod-coil diblock copolymers was achieved for the first time by TEMPO-mediated 'living' free radical polymerization of styrene and 2,5-bis [(4-methoxyphenyl)oxycarbonyl] styrene(MPCS). The block architecture of the two diblock copolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was confirmed by GPC, DSC studies and the formation of multimolecular micelles. (Author abstract) 10 Refs.

LIQUID CRYSTAL POLYMERS WITH TWO-DIMENSIONAL MESOGENIC UNITS

A series of 'liquid crystal polymers with two-dimensional mesogeuic units' were synthesized by the polycondensations of the monomer 2, 5-dihydroxybenzylidene-4-phenetidine with a diacid chloride selected from a series of α, ω-bis(4-chloroformylphenyloxy)carbonylalkues. This is the first series of polymers reported under the newly proposed concept 'liquid crystal polymers with two dimensional mesogenic units'.

SYNTHESIS AND CHARACTERIZATI0N OF POLYMETHACRYLATES BEARING HETEROCYCLIC AZO GROUP AND MESOGENIC GROUP FOR NONLINEAR OPTICS

The methacrylate monomers bearing mesogenic group and heterocyclicazo dye have been synthesized. The monomeric dye was copolymerized with the mesogenicmonomer using a free radical initiator to produce polymers useful for nonlinear optics. Themonomers and polymers were characterized by IR,;H-NMR, and UV-Vis spectra. Theaverage molecular weight （M;and M;） of the polymers were determined by gel permeationchromatography. The thermal properties of the polymers such as thermal stability andphase transition behavior were studied by thermogravimetric analysis, differential thermalanalysis, polarizing optical microscope and X-ray diffractometer. The results demonstratethat the synthesized polymers are crystalline polymers at room temperature and no liquidcrystalline phases were observed for all of them.

THE EFFECT OF SUBSTITUENT ON THE THERMAL PROPERTIES OF POLYESTERS CONSISTING OF AROMATIC TYPE SCHIFF BASE MESOGENIC UNITS AND POLYMETHYLENE SPACERS

Polyesters consisting of substituted aromatic type Schiff base mesogenic unit andpolymethylene spacers were synthesized and their thermal transitions and liquid crystallineproperties were studied. The liquid crystalline behaviour has been characterized by differentialscanning calorimetry (DSC) and optical polarizing microscopy. Structural broadening bysubstitution of methoxy group in 2, 2' positions of the mesogenic core produce polymers withlower transition temperatures. Polymers synthesized from ortho and meta substituted phenylenediamine did not form a liquid crystal phase.

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.

Phase behaviors of binary mixtures composed of banana-shaped and calamitic mesogens

In this work, five mixtures with different concentrations of banana-shaped and calamitic compounds have been prepared and subsequently studied by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction on non-oriented samples. The phase sequences and molecular parameters of the binary systems are presented.

SYNTHESIS AND MESOGENIC PROPERTY OF Pd-COORDINATING AZO-TYPE SIDE CHAIN LIQUID CRYSTALLINE POLYSILOXANE

A novel palladium-coordinating Azo-type liquid crystalline polysiloxane （Pd-AZLCP） has been synthesized by chelation reaction of polymeric ligand, Azo-type liquid crystalline polysiloxane（AZLCP）, with palladium dichloride and potassium chloride in the presence of tetrahydrofuran （THF） as reaction medium instead of dioxane/water system, which has been used since Cope first reported the synthesis of palladium-azobenzene in 1965 . The mesogenic behaviors examined by DSC, temperature-variable X-ray diffraction and polarizing microscopy indicate that the incorporation of Pd ions into the liquid crystal polymer can play a positive effect on the mesogenic property of the parent polymeric ligand. It is exhibited that the isotropization temperature T;is increased and the mesophase range ΔT has been widened, too.

SYNTHESIS OF MAIN CHAIN LIQUID CRYSTALLINE COPOLYESTERS WITH X-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4＇-（a;arhexanedioyloxy） dibenzoyl dichloride （MI）, 2,5-bis（p-octyloxybenzoyloxy） hydro-quinone （M2） and cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 （M3）. Monomer MI was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [η] of copolyesters ranges from 0.25-0.35. The monomers＇ structures were identified by using elemental analysis, IR, UV, ^1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHC13 at room temperature except cPg. The properties of copolyesters were investigated by using GPC, [η] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature （Tin）. The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 unit in the copolyesters.

SYNTHESIS OF LIQUID CRYSTALLINE COPOLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomers ...

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-shaped and rod-shaped mesogenic units were synthesized via solution condensation polymerizations of 4,4'-(alpha,omega-octanedioyloxy)-dibenzoyl dichlorides with 2,5-bis(p-octanoxy benzoyloxy)-hydroquinone and diphenol. All of the copolyesters showed thermotropic liquid crystalline behaviors through observations using DSC, polarized microscopy and X-ray diffraction. The melting point (T-m) and the isotropization temperature (T-i) change regularly with varying the content of diphenol unit in the copolymers.

SYNTHESIS AND CHARACTERIZATION OF COMB-LIKE POLYMERS BEARING HETEROCYCLIC AZO GROUP AND MESOGENIC GROUP

The synthesis and characterization of a series of novel comb-like polymethacrylates bearing heterocyclic azo group and mesogenic group are described. The thermal properties of the polymers such as thermal stability and phase transition behavior were investigated by thermogravimetric analysis, differential thermal analysis and polarizing optical microscopy techniques. The experimental results show that all the synthesized polymers do not exhibit liquid crystallinity except the homopolymer of the mesogenic monomer MAPB2 and the glass transition temperatures of the polymers increase with increasing content of azo moiety in polymers linearly.

SYNTHESIS OF SIDE-CHAIN LIQUID CRYSTALLINE POLYSILOXANE CONTAINING SCHIFF′S BASE MESOGENS WITH NO_2-END GROUP AND ITS BEHAVIOR IN A DC ELECTRIC FIELD

A side chain liquid crystalline copolysiloxane, which would show electro-optic effects as known from low mass liquid crystal, was synthesized by hydrosilylation reaction, and the two homologous monomers with different length spacers containing Schiff's base mesogen with—NO_2 terminated group were grafted toa polysiloxane main chain. Residual monomer in crude product is effective in reinforcing the response to an electric field over that of pure polymeric liquid crystal.

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

A series of liquid crystalline polymers with T-shaped two-dimensional mesogenic unitswere synthesized via low temperature solution polycondensation of 2-(4'-alkoxy-phenyl)hydroquinone with various diacyl dichlorides. The polymers were found to be nematic andshown thermotropic liquid crystalline behaviors through observations using DSC, polarizedmicroscopy and X-ray diffraction. The melting temperature T_m and the isotropizationtemperature T_i of the polymers change regularly with varying of the monomer structures.

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTAL POLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNITS(Ⅲ)

A new series of liquid crystal polyesters with T-shaped two-dimensional mesogenic units weresynthesized by melt polycondensation of the diacetates of 2-(4'-alkoxy -phenyl)-hydroquinones with 4,4'-alkylenedioxydibenzoic acid. The polymers were characterized by using polarized microscopy, DSC and X-ray diffraction. It was realized that all the polymers have nematic thermotropic liquid crystallinecharacteristics. The melting temperature (T_m) and isotropization temperature (T_i) of the polymers changeregularly with varying lengths of the alkoxy side group and the length of the alkylene group in the main chainin company with an even-odd effect. The mesophase temperature range also varies regularly with the polymerstructure. It is shown that the mesophase range has been widened.

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

Two series of new liquid crystalline polymers with T-shaped two-dimensional mesogenic units were synthesized by low temperature solution polycondensations of 4-substituted N-2, 5-dihydroxybenzylidene aniline monomers with different diacyl dichlorides. The polymers were found to be nematic and shown liquid crystalline behavior. The melting temperature T-m and the clearing temperature T-i of the polymers change regularly with varying of the monomer structures.

NITROXIDE-MEDIATED FREE RADICAL SYNTHESIS OF MESOGEN-JACKETED LIQUID CRYSTAL POLYMERS

The first TEMPO-mediated 'living' free radical polymerization of liquid crystalline monomer, 2, 5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), was carried out at 130 degrees C with BPO as an initiator. The molecular weight of the polymer can be varied from rather low values to high values while maintaining narrow polydispersity. It was observed that the polymerization of MPCS proceeded much faster than that of styrene. A tentative explanation for this fast polymerization was suggested.

SYNTHESIS OF A GROUP OF MESOGEN JACKETED LIQUID CRYSTAL POLYMERS

A group of the mesogen jacketed liquid crystal polymers based on the monomers 2,5-bis (4-substituted benzoyl)oxystyrenes are synthesized. The substituents include alkoxy, alkyl, and cyano groups. The synthesis and the primary characterization of the liquid crystal phase of the monomers and the polymers are described. While some of the monomers give smectic textures the polymers are found to be nematic above their melting or glass transition temperatures. Interestingly the unsubstituted monomer and its polymer poly 2,5-di( benzoyloxy ) styrene are also liquid crystalline. The single crystal structure of one of the monomers is also discussed.