Synthesis of a hexafluoropropylidene-bis(phthalic anhydride)-based polyimide and its conducting polymer composites with polypyrrole

A new electrically conducting composite film from polypyrrole and 4,4′-(hexafluoroisopropylidene)-bis(phthalic anhydride)-based polyimide was prepared. Pyrrole and the dopant ion can easily penetrate through the polyimide substrate and electropolymerize on the platinum (Pt) electrode due to the swelling of the polyimide on the metal electrode. The electrochemical properties of polypyrrole-polyimide (PPy/PI) composite films have been investigated by using cyclic voltammetry. The PPy/PI composite film is suitable for use as the electroactive material owing to its stable and controllable electrochemical properties. The electrical conductivity of composites falls in the range 0.0035–15 S/cm. Scanning electron micrograph, FTIR, and thermal studies indicate that PPy and PI form a homogeneous material rather than a simple mixture. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3009–3016, 1997     

Transmission electron microscopy of 3F/PMDA-polypropylene oxide triblock copolymer based nanofoams

Transmission electron microscopy was performed on a polymeric nanofoam material, derived from a triblock copolymer composed of a fluorinated polyimide center block, 3F/PMDA (derived from pyromelletic dianhydride (PMDA) and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (3F)) and polypropylene oxide (PO) end blocks. The cast and imidized polymer exhibits a microphase-separated morphology consisting of PO microdomains within a polyimide matrix. The final nanofoam material is obtained by decomposing PO microdomains into low molecular weight products, which diffuse out of the polyimide matrix leaving nanometer length scale voids. Ruthenium tetroxide staining prior to microscopy was used to enhance the contrast between the 3F/PMDA matrix and the PO microdomains or voids, which permitted a more detailed view of the microstructure of both the foamed and unfoamed materials. From the power spectra of the micrographs, spatial correlation between the PO microdomains in the unfoamed material and between the voids in the foam were found. An interdomain separation distance of ca. 37 nm was observed. Analysis of the image yielded an average area of 411 nm² for the PO domains. The analysis indicated that the PO domains were oblong, having average major and minor dimensions of 35 and 12.5 nm, respectively. An autocorrelation of the image showed that the domain center of masses were positioned 41 nm apart, in close agreement with the domain spacing (ca. 37 nm) found as described above. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1067–1076, 1997     

Covalently Linked,Transparent Silica–Poly(imide) Hybrids

Silica–poly(imide) hybrid materials have been developed which rely on interactions between the organic and inorganic phases to improve homogeneity. Using this method, transparent hybrids have been formed over all compositions studied. The hybrids show improved hardness and modulus with increasing silica content. Links between the two phases result in very finely divided microstructures. Hybrids such as these might be very important as barrier layers or scratch-resistant coatings. © 1997 John Wiley & Sons, Ltd.     

Characterization of vapor deposition polymerized polyimide thin films

Vapor deposition polymerized (VDP) polyimide (PI) thin films were prepared and characterized by using thermogravimetrical analysis (TGA), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR), and bending-beam techniques. The film properties investigated were thermal stability, wet-etching characteristics, surface topology, imidization characteristics, internal stress upon curing and thermal cycling, and hygroscopic stress upon moisture diffusion. Markedly different characteristics are observed for the VDP-PI films when comparing with the conventional ones. They seem denser in film structure and have better mechanical properties, but are somewhat less stable in thermal resistance. © 1996 John Wiley & Sons, Inc.     

High Tg polyimide nanofoams derived from pyromellitic dianhydride and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane

New routes for the synthesis of high T_g thermally stable polymer foams with pore sizes in the nanometer regime have been developed. Foams were prepared by casting well-defined microphase-separated block copolymers comprised of a thermally stable block and a thermally labile material. At properly designed volume fractions the morphology provides a matrix of the thermally stable material with the thermally labile material as the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis generating pores, the size and shape of which are dictated by the initial copolymer morphology. Triblock copolymers comprised of a high T_g, amorphous polyimide matrix with poly(propylene oxide) as the thermally decomposable coblock, were prepared. The copolymer synthesis was conducted through the poly(amic acid) precursor and subsequent cyclodehydration to the polyimide by either thermal or chemical means. Dynamic mechanical analysis confirmed microphase separated morphologies for all copolymers, irrespective of the propylene oxide block lengths investigated. Upon decomposition of the thermally labile coblock, a 9–18% reduction in density was observed, consistent with the generation of a foam which was stable to 400°C. © 1996 John Wiley & Sons, Inc.     

A fast-switching vertically-aligned liquid crystal device based on a multi-functional mesogenic photocrosslinker

Abstract

A vertically-aligned liquid crystal (LC) device with fast-switching LC molecules and excellent electro-optical properties is proposed. The proposed method employs a mixture of a polyimide to achieve the desired vertical alignment, and a mesogenic photocrosslinker to obtain the fast LC response. More specifically, the photocrosslinkers were photopolymerized by UV irradiation under an electric field to pre-tilt the LC molecules. In addition, upon increasing the number of functional groups in the photocrosslinker, faster switching properties were exhibited due to enhanced pre-tilting. Following UV irradiation, the proposed system also exhibited stable homeotropic alignment properties similar to those of conventional polyimides.     

基于苯醚型含氟二胺的聚酰亚胺膜材料的合成与表征

4,4′-二羟基二苯醚和2-氯-5-硝基三氟甲苯经Williamson反应得到4,4′-双(4-硝基-2-三氟甲基苯氧基)二苯醚;在Pd/C-水合肼还原作用下得到4,4′-双(4-氨基-2-三氟甲基苯氧基)二苯醚(p-6FAPE).采用3种苯醚型含氟二胺1,4-双(3-氨基-5-三氟甲基苯氧基)苯、1,4-双(4-氨基-2-三氟甲基苯氧基)苯和p-6FAPE分别与3,3′,4,4′-二苯醚四酸二酐(ODPA)和均苯四甲酸二酐通过两步法制备出6种含氟聚酰亚胺(PI),对其溶解性、热性能和光学性能进行研究.这些PI具有较好的溶解性,且具有良好的热稳定性;ODPA基PI在可见光波长范围具有优良的透明性,450 nm处的透光率超过80%.     

6FDA型聚酰亚胺的合成及其分子量调控

以4,40（六氟异丙烯）二酞酸酐（6FDA）为二酐单体,2,2-双（3胺基-4-羟基苯）六氟丙烷为二胺单体,采用“溶液缩聚-亚胺化反应”两步合成法,获得了可溶性聚酰亚胺材料。通过傅里叶变换红外光谱（FTIR）、凝胶色谱（GPC）、热重分析（TGA）、X射线衍射（XRD）等分析测试,考察了原料配比、亚胺化温度、亚胺化时间及催化剂等因素对产物重均分子量等特性参量的影响。结果表明：通过调节合成条件,该聚酰亚胺重均分子量可达4．5×10^4,具有优良的热稳定性,其起始分解温度高于490℃,且在NMP、DMF、DMAc、DMSO、THF、丙酮等有机溶剂中具有优良的溶解性能,能于80℃的低温下亚胺化制得,对材料的大批量制备具有重要意义。     

柔性交联型聚酰亚胺气凝胶的制备及性能

利用溶胶-凝胶反应制备了聚酰亚胺凝胶, 经过超临界干燥得到了聚酰亚胺气凝胶. 研究了固含量和交联剂比例对气凝胶性能的影响规律. 结果表明, 聚酰亚胺气凝胶的密度和线收缩率都随着固含量和交联剂比例的增加而增加; 随着固含量的增加, 气凝胶的室温热导率呈现出先降低再增加的趋势(0.026~0.033 W·m^-1·K^-1), 气凝胶的力学刚度和强度明显提升; 交联剂的加入, 可以提高材料的韧性, 断裂应变最高达21.7%; 制得的柔性聚酰亚胺气凝胶具有良好的热稳定性, 是满足尖端武器以及空间飞行器对于轻质、 柔性热防护要求的理想材料之一.