MORPHOLOGICAL AND KINETIC STUDIES OF PHASE TRANSITIONS OF A SIDE-CHAIN LIQUID CRYSTALLINE POLYMER

The morphological changes of a side-chain liquid-crystalline polymethacrylate during isotropization and liquid-crystallization transitions were studied by means of polarizing microscopy. These transitions were found to be composed of the initiation of a new phase at local places of the old phase matrix and the growth of the new phase: domains. The kinetics of the liquid-crystallization of the polymer from an isotropic melt to a smectic mesophase was also investigated. The isothermal process of the transition can be described by the Avrami equation. The values of the Avrami exponent were found to be around 2.6. which is lower than the value usually obtained for crystallization transition of polymers, but larger than that reported for liquid-crystallization transition of main-chain polymers. These results may indicate the difference in growth geometry of new phase during transition between crystallization and liquid-crystallization in general and between liquid-crystallization of main-chain and side-chain polymers. It was found that the liquid-crystallization of the used side-chain polymethacrylate may occur at small undercoolings with high transformation rate similar to that of main-chain polymers and small-molecule liquid crystals, while the crystallization of polymers can only proceed at large undercoolings. These phenomena can be explained by the idea that the surface free energy of nucleus during liquid-crystallization transition is less than that for crystallization, and evidence was obtained from analysis of the temperature dependence of the transformation rate.

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 mesophase transitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogens of three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture was observed in the transition temperature range. Similar to main-chain liquid crystalline polymers the transition process of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at local places 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.

Synthesis and Phase Behavior of Poly(1-alkyne) with Liquid Crystalline-induced Luminescence Enhancement

Poly（1-alkyne） with octoxy spacer —{[HC=C（CH2）8O—terphenyl—CN]}n—（PA8CN） and terphenyl liquid crystalline pendant was synthesized,and the effects of structure on the optical properties,especially the liquid crystallinity behavior of the polymer and monomer were investigated.The monomer was prepared in high yields（92.30%） by coupling and etherification reactions and successfully polymerized in the presence of Rh catalyst and Et3N cocatalyst in high yields with trans-rich（86.27%） stereoregular structure.Compared to the monomer showing mixed monolayer structure,its corresponding polymer PA8CN formed homogeneous monolayer arrangement.Upon photoexcitation,strong blue emission peak of PA8CN appeared at 413 nm[fluorescence quantum yield,ΦF = 68% when excited at 330 nm in tetrahydrofuran（THF） solution].Compared with its solid film photoexcitated at 330 nm at room temperature,the UV light-emitting band of PA8CN solid film from its liquid crystalline with liquid nitrogen quenched rapidly at 236 ℃ was red-shift 10 nm with higher intensity,which may be ascribed to the fact that the effectual conjugation and the order degree of the molecule in the liquid crystalline state of the polymer were enhanced,the energy loss caused by the thermal vibration was decreased,thus resulting in the observed hyperchromic effect.

STUDY OF CHIRAL SIDE CHAIN LIQUID CRYSTALLINE POLYMERS

Five kinds of side chain liquid crystalline polymers with a chiral component in the pendant group were synthesized and characterized by GPC, polarizing microscopy, DSC, X-ray diffraction ano Dielectric Relaxation Spectroscopy. The liquid crystalline behaviour of the polymers is affected by the length of flexible spacer, which links the mesogenic side chain to the polymer backbone and mesogenic moiety. The characteristic of smectic phase is observed for all the polymers.

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.

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.

Phase Behavior of the Ternary Solution Involving Rodlike and Random Coil Polymers

The present paper covers the phase behavior of poly(pbenzamide)(PBA)/Nylon 6/H 2SO 4 and poly(pphenylene terephthalamide) (PPTA)/Nylon 6/H 2SO 4 systems. The transition temperatures detected by the Depolarized Light Intensity measurements were used to construct the phase diagram in which the influence of temperature was shown. The enhanced depolarized light intensity observed in the ternary system suggests that the coil polymer chains may tend to be extended and contribute to the overall anisotropy of the liquid crystal phase.

STUDY ON CHIRAL LIQUID CRYSTALLINE POLYMERS WITH BIPHENYLENE AND AZOBENZENE AS THE MESOGENS

Chiral liquid crystalline polymers containing biphenylene and azobenzene as the mesogensand S(-)-2-methyl-1-butanol as the chiral end group were synthesized and characterized by DSC,POM and X-ray diffraction. These polymers show crystalline or glassy liquid crystalline phase atroom temperature. Most polymers show smectic A or highly ordered smectic phases abovemelting temperature.

SYNTHESIS AND CHARAOTERIZATION OF NOVEL THERMOTROPIO LIQUID ORYSTALLINE POLYESTERS BEARING NONLINEAR OPTICAL AZOBENZENE SIDE GROUP

A series of novel thermotropic liquid crystalline polyesters bearing nonlinear optical azobenzene side group were synthesized by high temperature solution polycondensation and their structures,thermal stability, phase transition behavior and crystallinity were characterized by IR,elemental analysis, TG-DTA, polarizing optical microscope (POM) equipped with a hot stage and X-ray diffraction techniques. The results demonstrate that all the synthesized polyesters exhibit nematic liquid crystalline phases and show relatively high glass transition temperatures and good thermal stability.

PVME/PS共混体系相分离行为的液态簧振动力学谱的研究

本研究利用自制的液态簧振动力学谱(RMS-L)技术研究了聚甲基乙烯基醚/聚苯乙烯(PVME/PS)二元共混物的玻璃化转变及相分离动力学过程,并选取了不同质量比样品,对每个样品从低温至高温的升降温循环测量。结果表明:(1)RMS-L方法可以灵敏地对不同混合比例的高分子共混体系玻璃化转变和相分离过程进行实时检测;(2)以纯PVME和纯PS玻璃化转变温度为基础,从11组待测样品中挑选组分比为5∶5的样品进行了分析,发现样品的玻璃化转变温度随着组分的变化而变化。而当温度达到某一点时样品会发生相分离。(3)当样品经过第二次升温时发现共混体系的玻璃化转变温度及相分离温度点均有变化,这说明在经过一次升温后样品已经被分为新的相;(4)结合不同比例样品的力学谱结果,发现共混体系相分离行为对时间和温度具有一定的依赖性,并且通过这种规律分析了高分子共混物相分离的动力学行为。

Synthesis and Liquid Crystalline Behavior of Side Chain Liquid Crystalline Polymers Containing Triphenylene Discotic Mesogens with Different Length Flexible Spacers

A series of side chain liquid crystalline polymers （SCLCPs） containing triphenylene （Tp） units in the side chains, denoted as PMTS （without spacer） and PMTnS （n = 2, 3, 4, 6, which is the number of the methylene units between the main chain and Tp moieties in the side chains）, with different lengths of spacers were synthesized through conventional free radical polymerization. The chemical structures of the monomers were confirmed by 1H/IaC-NMR, and the phase behaviors were examined by differential scanning calorimetry （DSC）, polarized optical microscopy （POM） and wide-angle X-ray diffraction （1D and 2D WAXD）. The molecular characterization of the polymers was performed with 1H-NMR, gel permeation chromatography （GPC） and thermogravimetric analysis （TGA）. The phase behaviors of the polymers have been investigated by a combination of techniques including DSC, POM, 1D and 2D WAXD. The results showed that the length of spacer has significant effects on the LC phase behavior of polymers. For PMTS and PMT2S, they displayed the columnar phase developed by the Tp moieties and the main chain as a whole due to the strong coupling effect of the Tp moieties and the main chain. For the PMT3S, PMT4S and PMT6S, they formed the symmetry hexagonal columnar （~n） phase owing to the decoupling effect. All of these indicated that the ＂decoupling effect＂ or ＂coupling effect＂ depended on the length of spacers, leading to the different LC phase formation mechanism.

Multiple Effects Tailoring the Self-organization Behaviors of Triphenylene Side-chain Liquid Crystalline Polymers via Changing the Spacer Length

Long-alkyl tail triphenylene （TP） side-chain liquid crystalline polymers （SCLCPs） with different spacer length （P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers） have been successfully synthesized via free radical polymerization. The differential scanning calorimetry （DSC）, polarized light microscopy （POM）, ultraviolet-visible spectroscopy （UV- Vis）, wide-angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP （m = 2, 3, 4） formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length （m） exceeded 4. In addition, the clearing points （Tis） of the polymers were above 300 ℃. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis （91 and 80 ℃ respectively）, originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure ofTP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.

Conformation of liquid crystalline state in interaction between chemical materials and biomembrane in terms of modern physics

A study by the technique of modern physics has been made on the conformation of the liquid crystalline state in the interaction between chemical materials and biomembrane. The experiments have proved that the biomembrane in the liquid crystalline state can be changed from the double layer phase into the non\|double layer phase due to the influence of the outside environment. Besides the common cubic and hexagonal phases, some more other complex middle phases are also included in these non\|double layer structures, namely the lamellar\|cubic structures, the lamellar\|hexagonal structures and the cubic\|hexagonal structures. It is found that chemical materials can make the biomembrane in the liquid crystalline state assume non\|double layer structures. Their ionic radius, the van der Waals force and electrostatic interaction between the amphiphilic molecules, the electric dipole moment and pH value all have some effects on the liquid crystalline structure of biomembrane.

P(VDF-TrFE)共聚物结晶性能研究进展

P(VDF-TrFE)凭借其柔性好、频率响应大、化学性能稳定和自发极化强度高,在柔性有机器件中具有广阔应用前景。聚合物的结晶性能直接决定其压电、铁电性能的强弱,本文综述了单体共聚比例、薄膜制备工艺条件及共混物类型与含量等因素对P(VDF-TrFE)共聚物结晶性能的影响,并简要阐述了各种因素对P(VDF-TrFE)结晶性能的影响机理。

Synthesis of Schiff Base-type Liquid Crystalline Crown Ethers Containing Dibenzo-18-Crown-6 Unit

The synthesis and characterization of novel Schiff base liquid crystalline crown ethers prepared from the inter-mediates 4-(4-alkoxylbiphenyl-4-carbonyl)benzaldehyde, cis- and trans-4,4-diaminodibenzo-18-crown-6 are de-scribed. The structure of these compounds have been well characterized by elemental analysis, IR, 1H NMR and MS spectroscopy. The liquid-crystalline behavior of these compounds was also inverstigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) with a heating stage and polarimetric analysis.

In situ Characterization of Phase Transition of Amorphous Poly(9,9-di-n-octyl-2,7-fluorene)Thin Film During Thermal Annealing

Amorphous poly(9,9-di-n-octyl-2,7-fluorene)(PFO)thin films were characterized in situ via thermal an- nealing based on grazing incidence X-ray diffraction(GIXRD)profiles,UV-visible absorption spectrophotometry,and Fourier transform infrared spectroscopy(FTIR).The results of GIXRD indicated that the amorphous phase transformed into a crystalline phase when the annealing temperature was higher than 80 ℃.Different outcomes were elicited for the intensities and d-spacings of the diffraction peaks below and above 80 ℃,which were attributed to the formation of the κ-phase.The mechanism of phase transition was revealed by in situ UV-visible absorption and FTIR spectra,whereby the rearrangement of the side chains was dominant and the movement of the main chains was minimal,even when the annealing temperature was lower than 80 ℃.In contrast,the rearrangement of the main chains was dominant when the temperature was higher than 80 ℃.

侧链型偶氮聚合物液晶在不同温度条件下的光致取向

在高于和低于玻璃化转变温度 (Tg)的温度范围内 ,研究了聚甲基丙烯酸 ( 6 [4 ( 4 氰基偶氮苯 )苯氧基 ]己酯 ) (Poly( 6 [4 ( 4 cyanophenylazo)phenoxy]hexylmethacrylate) (PM6ABCN) )聚合物膜的光致取向行为 .实验结果表明 ,在温度低于Tg 时 ,实验温度对取向速率没有影响 ;高于Tg 温度时 ,取向的速率随温度升高而变大 ,取向过程的表观活化能为 3 2 76kJ mol.通过对Tg 温度以下的光致取向进行分析 ,对光致取向过程提出了一个新的微相模型 ,微相内的温度能够达到Tg 以上 ,而实验中控制的样品宏观温度不变 ;高于Tg 温度时的光致取向过程受到宏观温度的控制 ,其表观活化能远远小于热致的各向同性相I(Isotropicphase,I)到向列相N(Nematicphase,N)相转变表观活化能 ( 3 40 2kJ mol) 。

端基含4个丁氧基苯介晶基元光致变色液晶树状物的合成、结构及液晶性研究

合成了周边含 4个丁氧基偶氮苯介晶基元 (M 5 )端基新的零代光致变色液晶树状物 (D0 ) ,并用元素分析、核磁共振、基质辅助激光解吸飞行时间质谱、红外、紫外、偏光显微镜、差示扫描量热 (DSC)和广角X射线衍射法 (WAXD)表征 .D0显示向列相 ,与M 5相同 ,树状物相态由介晶基元相态所决定 ,D0的相行为 :K13 8N14 7I14 5N118K .对零代 (D0 )、一代 (D1)、二代 (D2 )和三代 (D3 )液晶树状物的清亮焓、清亮熵。

一种侧链液晶高分子的合成与表征

合成了一种主链为甲基丙烯酸酯 ,侧链是三个苯环以酯键相连的介晶基元 ,柔性间隔段为两个亚甲基的新的侧链液晶高分子 .聚合物和单体的化学结构、液晶相转变和液晶态织构采用红外光谱、核磁共振、偏光显微镜、差热分析和广角X光衍射进行了表征 .研究表明 ,单体呈现近晶相和向列相两个液晶相 ,聚合物在很宽的温度范围内呈向列相 .