Semi-alicyclic colorless and transparent polyimide (CPI) films usually suffer from the high linear coefficients of thermal expansion (CTEs) due to the intrinsic thermo-sensitive alicyclic segments in the polymers. A series of semi-alicyclic CPI films containing rigid-rod amide moieties were successfully prepared in the current work in order to reduce the CTEs of the CPI films while maintaining their original optical transparency and solution-processability. For this purpose, two alicyclic dianhydrides, hydrogenated pyromellitic anhydride (HPMDA, I), and hydrogenated 3,3’,4,4’-biphenyltetracarboxylic dianhydride (HBPDA, II) were polymerized with two amide-bridged aromatic diamines, 2-methyl-4,4’-diaminobenzanilide (MeDABA, a) and 2-chloro-4,4’-diaminobenzanilide (ClDABA, b) respectively to afford four CPI resins. The derived CPI resins were all soluble in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Flexible and tough CPI films were successfully prepared by casing the PI solutions onto glass substrates followed by thermally cured at elevated temperatures from 80 °C to 250 °C. The MeDABA derived PI-I_a (HPMDA-MeDABA) and PI-II_a (HBPDA-MeDABA) exhibited superior optical transparency compared to those derived from ClDABA (PI-I_b and PI-II_b). PI-I_a and PI-II_a showed the optical transmittances of 82.3% and 85.8% at the wavelength of 400 nm with a thickness around 25 μm, respectively. Introduction of rigid-rod amide moiety endowed the HPMDA-PI films good thermal stability at elevated temperatures with the CTE values of 33.4 × 10⁻⁶/K for PI-I_a and 27.7 × 10⁻⁶/K for PI-I_b in the temperature range of 50–250 °C. Comparatively, the HBPDA-PI films exhibited much higher CTE values. In addition, the HPMDA-PI films exhibited good thermal stability with the 5% weight loss temperatures (T_5%) higher than 430 °C and glass transition temperatures (T_g) in the range of 349–351 °C.

Protection of polymeric materials from the atomic oxygen erosion in low-earth orbit spacecrafts has become one of the most important research topics in aerospace science. In the current research, a series of novel organic/inorganic nanocomposite films with excellent atomic oxygen (AO) resistance are prepared from the phosphorous-containing polyimide (FPI) matrix and trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP–POSS) additive. The PI matrix derived from 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,5-bis[(4-amino- phenoxy)phenyl]diphenylphosphine oxide (BADPO) itself possesses the self-healing feature in AO environment. Incorporation of TSP–POSS further enhances the AO resistance of the FPI/TSP composite films via a Si–P synergic effect. Meanwhile, the thermal stability of the pristine film is maintained. The FPI-25 composite film with a 25 wt % loading of TSP–POSS in the FPI matrix exhibits an AO erosion yield of 3.1 × 10⁻²⁶ cm³/atom after an AO attack of 4.0 × 10²⁰ atoms/cm², which is only 5.8% and 1.0% that of pristine FPI-0 film (6FDA-BADPO) and PI-ref (PMDA-ODA) film derived from 1,2,4,5-pyromellitic anhydride (PMDA) and 4,4’-oxydianline (ODA), respectively. Inert phosphorous and silicon-containing passivation layers are observed at the surface of films during AO exposure.

In the current work, a series of black polyimide (PI) films with excellent thermal and dimensional stability at elevated temperatures were successfully developed. For this purpose, two aromatic diamines including 4,4′-iminodianline (NDA) and 2-(4-aminophenyl)-5- aminobenzimidazole (APBI) were copolymerized with pyromellitic dianhydride (PMDA) to afford PIs containing imino groups (–NH–) in the molecular structures. The referenced PI film, PI-ref, was simultaneously prepared from PMDA and 4,4′-oxydianiline (ODA). The introduction of imino groups endowed the PI films with excellent blackness and opaqueness with the optical transmittance lower than 2% at the wavelength of 600 nm at a thickness of 25 μm and lightness (L^*) below 10 for the CIE (Commission International Eclairage) Lab optical parameters. Meanwhile, the introduction of rigid benzimidazole units apparently improved the thermal and dimensional stability of the PI films. The PI-d film based on PMDA and mixed diamines (NDA:APBI = 70:30, molar ratio) showed a glass transition temperature (T_g) of 445.5 °C and a coefficient of thermal expansion (CTE) of 8.9 × 10⁻⁶/K in the temperature range of 50 to 250 °C, respectively. It is obviously superior to those of the PI-a (PMDA-NDA, T_g = 431.6 °C; CTE = 18.8 × 10⁻⁶/K) and PI-ref (PMDA-ODA, T_g = 418.8 °C; CTE: 29.5 × 10⁻⁶/K) films.

A new methodology for enhancing the solvent resistance of electrospun polyimide (PI) ultrafine fibrous mat (UFM) was investigated in the current work. For this purpose, a negative intrinsically photosensitive polyimide (PSPI) resin was prepared by the one-step high- temperature polycondensation procedure from 3,3’,4,4’-benzophenonetetracarboxylic dianhydride (BTDA) and α,α-bis(4-amino-3,5-dimethylphenyl)phenylmethane (PTMDA). The PI varnish, by dissolving the derived PI (BTDA-PTMDA) resin in N,N-dimethylacetamide (DMAc) at a solid of 20 wt %, was used as the starting material for the standard electrospinning (ES) and ultraviolet-assisted ES (UVAES) fabrications, respectively. The 365 nm wavelength of the high-pressure mercury lamp ultraviolet (UV) irradiation induced the photocrosslinking reaction in the PSPI mat. Solubility tests indicated that the PI UFM fabricated by standard ES procedure showed poor DMAc resistance, while the one by UVAES (PI-UV) exhibited excellent resistance to DMAc.

Enhancement of flame retardancy of a colorless and transparent semi-alicyclic polyimide (PI) film was carried out by the incorporation of phosphazene (PPZ) flame retardant (FR). For this purpose, PI-1 matrix was first synthesized from hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA) and 4,4′-oxydianiline (ODA). The soluble PI-1 resin was dissolved in N,N-dimethylacetamide (DMAc) to afford the PI-1 solution, which was then physically blended with PPZ FR with the loading amounts in the range of 0–25 wt.%. The PPZ FR exhibited good miscibility with the PI-1 matrix when its proportion was lower than 10 wt.% in the composite films. PI-3 composite film with the PPZ loading of 10 wt.% showed an optical transmittance of 75% at the wavelength of 450 nm with a thickness of 50 μm. More importantly, PI-3 exhibited a flame retardancy class of UL 94 VTM-0 and reduced total heat release (THR), heat release rate (HRR), smoke production rate (SPR), and rate of smoke release (RSR) values during combustion compared with the original PI-1 film. In addition, PI-3 film had a limiting oxygen index (LOI) of 30.9%, which is much higher than that of PI-1 matrix (LOI: 20.1%). Finally, incorporation of PPZ FR decreased the thermal stability of the PI films. The 10% weight loss temperature (T_10%) and the glass transition temperature (T_g) of the PI-3 film were 411.6 °C and 227.4 °C, respectively, which were lower than those of the PI-1 matrix (T_10%: 487.3 °C; T_g: 260.6 °C)

Uniform alignment of rigid-rod liquid crystal (LC) molecules under applied voltage is critical for achievement of high-quality display for thin-film transistor-driven liquid crystal display devices (TFT-LCDs). The polymeric components that can induce the alignment of randomly aligned LC molecules are called alignment layers (ALs). In the current work, a series of organo-soluble polyimide (SPI) ALs were designed and prepared from an alicyclic dianhydride, hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA), and various aromatic diamines, including 4,4′-methylenedianiline (MDA) for SPI-1, 4,4′-aminodianiline (NDA) for SPI-2, 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane (TMMDA) for SPI-3, and 3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane (DMDEDA) for SPI-4. The derived SPI resins were all soluble in N-methyl-2-pyrrolidone (NMP). Four SPI alignment agents with the solid content of 6 wt.% were prepared by dissolving the SPI resins in the mixed solvent of NMP and butyl cellulose (BC) (NMP/BC = 80:20, weight ratio). Liquid crystal minicells were successfully fabricated using the developed SPI varnishes as the LC molecule alignment components. The SPI ALs showed good alignment ability for the LC molecules with the pretilt angles in the range of 1.58°–1.97°. The LC minicells exhibited good optoelectronic characteristics with voltage holding ratio (VHR) values higher than 96%. The good alignment ability of the SPI ALs is mainly attributed to the good comprehensive properties of the SPI layers, including high volume resistivity, high degree of imidization at the processing temperature (230 °C), good rubbing resistance, good thermal stability with glass transition temperatures (T_gs) higher than 260 °C, and excellent optical transparency with the transmittance higher than 97% at the wavelength of 550 nm.