基于萘二胺和醚酮结构的高性能聚合物的合成

本文成功制备了新型的1,5-二[4-(4-氨基苯氧基)]苯羰基-2,6-二甲氧基萘大体积单体,并且通过室温反应制得了具有一定分子量的含有酮醚萘结构的聚甲亚胺和聚酰亚胺。新型聚合物具有高Tg,高热稳定性,高模量,良好的溶解性能和成膜性。     

可溶性聚酰亚胺的制备及其在液晶显示器上的潜在应用

以3,5-二硝基苯甲酰氯和4-羟基联苯为原料,合成了功能性二胺单体3,5-二氨基苯甲酸联苯酯(DABBE).用此单体与3,3′-二甲基-4,4′-二氨基二苯甲烷(DMMDA)、3,3′,4,4′-二苯醚四甲酸二酐(ODPA)共缩聚,采用低温缩聚-化学亚胺化的方法,通过调节共聚物组成制备了5种聚酰亚胺(PI).利用FT-IR、NMR、UV-Vis与DSC等手段对合成二胺单体及聚酰亚胺进行了结构表征和性能测试;研究了其溶解性能、透光性能、取向性能和耐热性能.结果表明,5种聚酰亚胺均可溶于NMP、DMF等极性溶剂;对液晶分子取向时的预倾角随DABBE的比例增加而增大,可达1.8°.但当DABBE的比例增加时,PI的分子量降低,将影响其成膜性能.此外,实验所得的PI透过率大于80%,玻璃化转变温度在220℃以上.     

乙烯基二联苯单体的螺旋选择性自由基聚合

为了深入理解乙烯基二联苯单体自由基聚合过程中的手性传递,进行了手性单体(+)-2-[(S)-异丁氧羰基-5-(4′-己氧基苯基)苯乙烯、非手性单体2-丁氧羰基-5-(4′-己氧基苯基)苯乙烯的均聚反应及它们二者的共聚反应,探讨了聚合温度和溶剂性质对手性单体均聚物旋光活性、手性单体含量对共聚物旋光活性以及聚合反应溶剂的超分子手性对共聚物旋光活性的影响.研究发现,降低聚合温度、采用液晶性反应介质有利于得到旋光度大的聚合物;少量手性单体的引入即可诱导共聚物形成某一方向占优的螺旋构象,比旋光度随手性单体的含量增加呈线性增长;在胆甾相液晶中制备的非手性单体聚合物不具有光学活性.这些结果表明,该类乙烯基二联苯聚合物具有动态螺旋构象,其光学活性主要依赖于主链的立构规整度和侧基不对称原子的手性.     

侧链含邻苯二甲酰亚胺的聚酰亚胺液晶垂直取向剂的制备与表征

以邻苯二甲酰亚胺和溴代正辛烷为原料,合成了功能性二胺单体N-辛基-4(3,5-二氨基苯甲酰基)-氨基邻苯二甲酰亚胺(D8).用此单体与3,3’-二甲基-4,4’-二氨基二苯甲烷(DMMDA)、3,3’,4,4’-二苯醚四甲酸二酐(ODPA)共缩聚,采用低温缩聚-化学亚胺化方法,通过调节共聚物组成制备了5种聚酰亚胺(PI).利用FTIR、NMR、UV-Vis与DSC等手段对合成的二胺单体及聚酰亚胺进行了结构表征和性能测试;研究了其摩擦取向性能、透光性能、溶解性能和耐热性能.结果表明,5种聚酰亚胺均可溶于常见极性溶剂,如NMP、THF等;随着D8含量的增加,PI膜对液晶分子取向时的预倾角逐渐增大至垂直,当D8含量大于20%,且经过5次摩擦后,预倾角仍能保持在89°以上.此外实验所得PI透过率大于80%,玻璃化转变温度在260℃以上.     

3，5—二氨基苯甲酸—4′—联苯酯含液晶侧链的聚酰亚胺的合成与表征

合成了含液晶基元侧基的二氨基化合物－3,5－二氨基苯甲酸－4′－联苯酯,并以3,3′-4,4′－二苯醚四羧酸二酐（ODPA）、二氨基二本醚（ODA）为共聚单体,制备了具仍液晶侧链原位复合自增强功能的新型聚酰亚胺（PI）薄膜材料,这种含液晶基元侧链的PI能溶 在极性非质子有机溶剂中,显示出良好的可加工性能,由于液晶基元侧链的原位复合自增强作用,该类膜材料显示出良好的力学性能和热稳定性在热台偏光显微镜下观察,该类聚合物在较高的温度区域内显示液晶行为,并呈现向相织构。     

3,5-二氨基苯甲酸-4′-联苯酯及含液晶侧链的聚酰亚胺的合成与表征

合成了含液晶基元侧基的二氨基化合物——— 3,5 二氨基苯甲酸 4′ 联苯酯 ,并以 3,3′ 4,4′ 二苯醚四羧酸二酐 (ODPA)、二氨基二苯醚 (ODA)为共聚单体 ,制备了具有液晶侧链原位复合自增强功能的新型聚酰亚胺 (PI)薄膜材料 .这种含液晶基元侧链的PI能溶解在极性非质子有机溶剂中 ,显示出良好的可加工性能 .由于液晶基元侧链的原位复合自增强作用 ,该类膜材料显示出良好的力学性能和热稳定性能在热台偏光显微镜下观察 ,该类聚合物在较高的温度区域内显示液晶行为 ,并呈现向列相织构     

不同比例的s-BPDA/i-BPDA型聚酰亚胺共聚结构与性能关系

由不同比例的二酐单体3,3′,4,4′-联苯四酸二酐(s-BPDA)/2,2′,3,3′-联苯四酸二酐(i-BPDA)与二胺单体4,4′-二氨基二苯醚(4,4′-ODA)制得了一系列共聚可溶聚酰亚胺. 采用DSC 、TGA和拉伸等测试方法对所得共聚聚酰亚胺进行了表征, 实验结果表明, 所得聚酰亚胺具有优异的力学性能和热稳定性, 并且随着i-BPDA含量的增加, 聚酰亚胺的溶解性提高, 玻璃化转变温度(Tg)升高, 中间体聚酰胺酸的固有黏度降低.     

含二氮杂萘酮结构磺化聚酰亚胺共聚物的合成及其膜性能研究

将磺化二胺单体4,4′-二(4-氨基苯氧基)联苯-3,3′-二磺酸(BAPBDS),含二氮杂萘酮结构的二胺1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(DHPZDA)和1,4,5,8-萘四甲酸二酐(NTDA)进行缩合聚合反应,通过改变磺化二胺单体BAPBDS的含量,合成了一系列不同磺化度的聚酰亚胺(SPIs).采用FT-IR,1H-NMR表征了聚合物的结构,热重分析仪(TGA)研究了聚合物的耐热稳定性.以间甲酚为溶剂,通过溶液浇铸法成膜研究了该系列聚合物膜的性能.结果表明,与其它磺化聚酰亚胺相比,该系列磺化聚酰亚胺的溶解性以及在高温下(80℃)水解稳定性有较大提高.     

聚酰亚胺类液晶光定向层材料的研究

经含有羟基的二胺单体HAB与二酐单体 4 ,4′ (六氟异丙基 ) 双邻苯二甲酸酐 ( 6FDA)的缩聚反应 ,制备了含有羟基的先驱聚合物PI OH ,通过PI OH上羟基与肉桂酰氯的酯化反应 ,制备了侧链带有肉桂酸酯基团的光敏聚酰亚胺PI CI.用氢核磁共振 ( 1H NMR)分析、傅立叶红外光谱 (FTIR)分析等表征了上述聚合物的结构与感光性能 .用紫外 可见光谱 (UV Vis)等方法研究了PI CI的光交联反应 .聚合物PI CI旋镀膜经线性偏振光聚合技术 (LPP)处理并装配得到的液晶盒可使液晶分子很好地定向沿面排列 .上述实验表明 ,本文所合成的聚酰亚胺定向层材料是一种新的液晶光定向层材料     

各向异性光交联作用对液晶在起伏光栅表面的取向影响

以含肉桂酸基团的光敏聚酰亚胺为"墨水",通过软印刷技术制备了一种新型的可进一步光交联的表面起伏光栅,研究了各向异性光交联对光栅热稳定性和光栅诱导液晶取向的影响.研究结果表明,在经过紫外光交联后,光栅的热稳定性有较大提高,在经过高于未交联聚酰亚胺的玻璃化转变温度31℃处理2 h后,光栅形貌未发生变化.曝光前后光栅都能诱导液晶分子在表面均一沿面排列.当线性偏振紫外光的偏振方向与光栅沟槽垂直时,光交联能促进光栅对液晶的定向能力,反之则降低的定向能力.通过改变辐照光的偏振方向,调节光栅深度,能控制液晶分子在光栅上的取向方向.将这种软印刷得到的光栅用作液晶定向层,不仅可具有更好的热稳定性和定向能力,还可以调节液晶分子在光栅上的取向方向,实现多畴取向.     

Polyimides with main-chain photosensitive groups: Synthesis, characterization and their properties as liquid crystal alignment layers

In this work, a series of polyimides containing main-chain chalcone groups and side-chain cinnamate or acetate groups were synthesized. In the synthetic route, three dianhydride monomers were prepared by the reactions of 1,3-dihydro-1,3-dioxoisobenzofuran-5-carbonyl chloride with 1,3-bis(4-hydroxylphenyl)prop-2-en-1-one, 1,3-bis(4-(2-hydroxyethyl)phenyl)prop-2-en-1-one, and 1,3-bis(4-hydroxyphenyl)-pent-1-en-3-one-4-en, respectively. The precursor polyimides were obtained by the polycondensation of the dianhydride monomers with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and the in situ imidization. After the polymerization, the final products were obtained by introducing the side groups through the reactions of the polyimide precursors with cinnamoyl chloride or acetic anhydride. The chemical structures and properties of the polyimides were characterized by elemental analysis, ¹H NMR, ¹³C NMR, FTIR, GPC, and thermal analysis. The polyimides show high thermal stability and good solubility in aprotic polar organic solvents. The polyimides can undergo sensitive [2+2] photocycloaddition reaction upon the UV light irradiation. After irradiation with linearly polarized UV light, the polyimide thin films can induce 5CB liquid crystal molecules to homogeneously align in the liquid crystal cells. Both the alignment ability and pretilt angles of the molecular orientation depend on the chemical structures of the polyimides.     

Flow behaviours of liquid crystal droplets on polyimide alignment layers

The flow behaviours of liquid crystal droplets on polyimide alignment layers and during assembling between two substrates have been directly observed. The droplet shape became elliptical with time on the rubbed polyimide layer, where the major axis of the elliptical droplet was parallel to the rubbing direction. Rubbing enhanced the wettability between the liquid crystal and the polyimide layer. During the assembling process, the liquid crystal droplets elliptically splayed out between two substrates assembled antiparallel. The liquid crystal molecules preferentially flowed parallel to the rubbing direction in a two-step flow mode; the droplet diameter slowly increased at the first step, and then it rapidly increased at the second step. The two-step flow of the droplet proved to be due to the thickness of the droplet dependent on the rubbing strength.     

Relationship between alignment layer polymer surface structures and liquid crystal display parameters

The polar alignment layer (AL) surface provided relatively small liquid crystal (LC) pretilt angles while polyimides with long alkyl side chains gave relatively large LC pretilt angles. The results suggest that LC pretilt angles, in addition to an anchoring effect, are greatly affected by both electronic and steric interactions between LC molecules and a polyimide alignment layer surface. Rubbing with a cotton cloth induces functional groups, side chains, and repeat units at the surface of a liquid crystal polyimide AL to re-orient. It was discovered that rubbing induced polar functional groups and repeat units to re-orient out-of-the-plane of the surface, and it made non-polar aliphatic side chains partially re-orient inwards, toward the bulk of the film.     

Synthesis of novel aromatic polyimides containing bulky side chain for vertical alignment liquid crystals

In this study, a novel 4-（4-octyloxybenzoyloxy）biphenyl-3′,5′-diaminobenzoate and polyimides based on it were synthesized. The polyimide with mesogenic unit side chain exhibited excellent vertical alignment for nematic liquid crystal （LC）. The pretilt angles of LCs above 89° were kept after the rubbing process with 220 mm rubbing strength. The polyimide films as the alignment layer were baked at 120℃ for 12 h, the vertical alignment of LCs was still uniform and stable. Meanwhile, the UV-vis spectra of the noyel polyimide films showed the high transparency in a visible wave length.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Effect of photoreactivity of polyimide on the molecular orientation of liquid crystals on photoreactive polymer/polyimide blends

We prepared blend alignment layers from polymethacrylate with coumarin side chains (PMA-g-coumarin) and polyimides for the orientation of liquid crystals (LCs) using linearly polarized ultraviolet (UV) irradiation. We used two different polyimides, namely 4,4'-(hexafluoro-isopropylidene) diphthalic anhydride-3,5-diamino-benzoic acid (6FDA-DBA) and pyromellitic dianhydride-4,4'-oxydianiline (PMDA-ODA). It was found that the molecular orientation of the LC depended on the type of polyimide in the blend alignment layer. The thermal stability of the LC orientation was enhanced regardless of the type of polyimide, while the direction of LC orientation was different for each type of polyimide. The photoreactivity of the polyimide was a very important factor in determining the molecular orientation of the LC on the blend alignment layer. This may be attributed to the different mechanisms of LC orientation on PMA-g-coumarin and polyimide induced by the polarized UV irradiation. The direction of the LC orientation could be changed by controlling the photoreaction of the polyimides using the appropriate UV filter for the polarized UV irradiation.     

Synthesis of new aromatic polyimides with various side chains containing a biphenyl mesogen unit and their abilities to control liquid-crystal alignments on the rubbed surface

New poly(m-phenylene 4,4′-oxydiphthalimide)s containing various side chains, such as 6-(4-biphenylmethoxy)hexyloxy group and 6-(phenylphenoxy)hexyloxy isomers, were synthesized, giving thin films of a high quality. All the polyimides apparently were almost amorphous, but exhibited short-range ordering in some extent, depending on the side chains. By incorporating side chains, the thermal properties, including stability, thermal expansivity, and glass transition temperature, were generally degraded, whereas the optical and dielectric properties were improved. All the polyimides exhibited a good rubbing processability and excellent performance in the controlling of both the alignment and the pretilt of LC molecules in the LC cell. The pretilt angle of LC molecules was easily achieved in a wide-angle range of 8–27°, depending upon the rubbing density as well as the incorporated side chains. The pretilting of LC molecules was very sensitive to all the molecular parameters (namely, the flexibility of polymer chain backbone as well as the isomeric structure of biphenyl mesogen end group, spacer length, and spacer conformation in the side chain) in the polyimide, in addition to the rubbing process. In particular, the side chains, which are much shorter in length than the long alkyl side chains in the polyimides being used widely as LC alignment layers, were evident to involve effectively in the alignment of and the pretilt of LC molecules, which are highly desired in the LC display industry. This might mainly be attributed to a strong interaction between the biphenyl mesogen end group of the side chain and the LC molecule. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2909–2921, 1999     

Hysteresis behaviour of the nematic-cholesteric phase transition for liquid crystals on polyimide films without use of the rubbing technique

The hysteresis behaviour of the nematic-cholesteric phase transition in liquid crystals is closely connected with the alignment of the liquid crystal molecules on the surfaces of treated solid substrates. We have investigated the hysteresis as a function of rubbing strength, using rubbing technology that controls the orientation of the liquid crystal molecules. The surface alignment direction contributes to the hysteresis width, is not dependent on rubbing strength, and is only slightly related to pretilt angles. A no-rubbing treatment, that is, random alignment, is important in-order to create a large hysteresis width on homogeneously aligned polyimide films.     

Effect of photoreactivity of polyimide on the molecular orientation of liquid crystals on photoreactive polymer/polyimide blends

We prepared blend alignment layers from polymethacrylate with coumarin side chains (PMA-g-coumarin) and polyimides for the orientation of liquid crystals (LCs) using linearly polarized ultraviolet (UV) irradiation. We used two different polyimides, namely 4,4′-(hexafluoro-isopropylidene) diphthalic anhydride-3,5-diamino-benzoic acid (6FDA-DBA) and pyromellitic dianhydride-4,4′-oxydianiline (PMDA-ODA). It was found that the molecular orientation of the LC depended on the type of polyimide in the blend alignment layer. The thermal stability of the LC orientation was enhanced regardless of the type of polyimide, while the direction of LC orientation was different for each type of polyimide. The photoreactivity of the polyimide was a very important factor in determining the molecular orientation of the LC on the blend alignment layer. This may be attributed to the different mechanisms of LC orientation on PMA-g-coumarin and polyimide induced by the polarized UV irradiation. The direction of the LC orientation could be changed by controlling the photoreaction of the polyimides using the appropriate UV filter for the polarized UV irradiation.