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Two organo‐soluble polyimide (PI) resins were prepared from a tricyclic fluoro‐containing dianhydride 9,9‐bis(trifluoromethyl)xanthene‐2,3,6,7‐tetracarboxylic dianhydride (6FCDA) and aromatic diamine of 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (BDAF) for PI‐IIa and 1,3‐bis(3‐aminophenoxy)benzene (133APB) for PI‐IIb, respectively. For comparison, two analogous PIs were prepared from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and the same diamines to afford PI‐Ia (6FDA‐BDAF) and PI‐Ib (6FDA‐133APB), respectively. Incorporation of the rigid and planar xanthene units in the 6FCDA‐PIs obviously decreased the solubility of the resins in organic solvents. Flexible and tough PI films were fabricated from the PI solutions in N,N‐dimethylacetamide (DMAc). The PI films derived from the rigid and planar 6FCDA dianhydride exhibited obviously enhance thermal stability, and high‐temperature dimensional stability. For example, PI‐IIa (6FCDA‐BDAF) showed the glass transition temperature (Tg) and coefficient of linear thermal expansion (CTE) values of 311.5°C and 50.5 × 10−6/K, respectively, which were all superior to those of the PI‐Ia counterpart (Tg = 264.6°C; CTE = 55.4 × 10−6/K). In addition, the 6FCDA‐PI films maintained the intrinsically excellent optical transparency of the fluoro‐containing PI films and showed the comparable optical properties to those of the 6FDA‐PI films. As for the properties highly related to the space applications, all the PI films exhibited low solar absorptivity (α) values of 0.18–0.20 and the good thermal emissivity (ε) values in the range of 0.68–0.70. PI‐Ia (6FDA‐BDAF) and PI‐IIa (6FCDA‐BDAF) films showed the similar atomic oxygen erosion behaviors with the standard Kapton® type of PI film derived from pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA). [ABSTRACT FROM AUTHOR]

Colorless and transparent polyimide (CPI) films with good atomic oxygen (AO) resistance and high thermal endurance are highly required in low earth orbit (LEO) space exploration. Conventional CPI films based on fluoro-containing 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) have been widely used in space applications. However, the AO erosion yields and glass transition temperatures (Tg) of the 6FDA-based CPI films have to be modified in order to meet the severe serving environments. In the current work, novel CPI films based on a multi-ring fluoro-containing 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylicdianhydride (6FCDA) monomer were developed. In order to enhance the AO resistance of the derived CPI film, a phosphorus-containing aromatic diamine, 2,5-bis[(4-aminophenoxy)phenyl]diphenylphosphine oxide (BADPO) was used to polymerize with the dianhydride to create the organo-soluble resin. Then, two phosphorus-containing CPI films (PPI), including PPI-1 (6FDA-BADPO) and PPI-2 (6FCDA-BADPO) were prepared by thermally curing of the PPI solutions at elevated temperatures. The PPI films maintained good optical transparency with transmittance values over 80% at a wavelength of 450 nm. PPI-2 exhibited a Tg value of 311.0 °C by differential scanning calorimetry (DSC) measurement, which was 46.7 °C higher than that of the PPI-1 counterpart (Tg = 264.3 °C). In addition, the PPI-2 film showed a coefficient of linear thermal expansion (CTE) value of 41.7 × 10−6/K in the range of 50~250 °C, which was apparently lower than that of the PPI-1 sample (CTE = 49.2 × 10−6/K). Lastly, both of the two PPI films exhibited good AO resistance with the erosion yields (Ey) of 6.99 × 10−25 cm3/atom for PPI-1 and 7.23 × 10−25 cm3/atom for PPI-2 at an exposure flux of 5.0 × 1020 atoms/cm2. The Ey values of the current PPI films were obviously lower than that of the standard polyimide (PI) film based on pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) (Ey = 3.0 × 10−24 cm3/atom). [ABSTRACT FROM AUTHOR]

Colorless and transparent semi‐alicyclic fluoro‐containing polyimide (PI) nanocomposite films with enhanced high‐temperature dimensional stability and sustained optical transparency were designed and prepared via incorporation of nano‐sized colloidal silica (SiO2) fillers into the PI matrix derived from hydrogenated pyromellitic dianhydride (HPMDA) and 2,2′‐bis[(4‐aminophenoxy)phenyl]hexafluoropropane (BDAF). The derived PI composite films, abbreviated as 6FCPI‐X in which X stands for the weight percent of the SiO2 in the composite films, exhibited superior thermal and comparable optical properties to the pristine 6FCPI‐0 (6FDA‐BDAF) matrix film. For example, as for the thermal properties, 6FCPI‐35 composite film showed a glass transition temperature (Tg) of 279.1°C and a residual weight ratio at 750°C (Rw750) of 66.1%, which were apparently higher than those of 6FCPI‐0 matrix (Tg = 272.2°C; Rw750 = 47.1%). More importantly, the 6FCPI/SiO2 nanocomposite films showed obviously lower linear coefficients of thermal expansion (CTE) values as compared with that of the 6FCPI‐0 matrix. 6FCPI‐35 composite film showed a CTE value of 36.1 × 10−6/K in the temperature range of 50–250°C, which was lower than half of that of the 6FCPI‐0 matrix (CTE = 77.9 × 10−6/K) in the same range of temperature. In addition, incorporation of nano‐sized colloidal SiO2 particles basically maintained the intrinsically good optical properties of the pristine 6FCPI‐0 matrix film. 6FCPI‐35 composite film showed the optical transmittances of 81.7%, 85.3%, and 87.2% at the wavelength of 400 nm (T400), 450 nm (T450), and 500 nm (T500), respectively, which were in the same level with those of the 6FCPI‐0 film (T400 = 84.0%; T450 = 86.3%; T500 = 87.6%). The 6FCPI series of nanocomposite films also exhibited similar CIE Lab color parameters, including the yellow indices (b*) lower than 2.0 and haze values lower than 1.0%. [ABSTRACT FROM AUTHOR]

Polymeric optical films with light colors, good optical transparency and high thermal resistance have gained increasing attention in advanced optoelectronic areas in recent years. However, it is somewhat inter-conflicting for achieving the good optical properties to the conventional thermal resistant polymers, such as the standard aromatic polyimide (PI) films, which are well known for the excellent combined properties and also the deep colors. In this work, a series of wholly aromatic PI films were prepared via the polycondensation chemistry of one fluorene-containing dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (FDAn) and several aromatic diamines with amide linkages in the main chain, including 9,9-bis [4-(4-aminobenzamide)phenyl]fluorene (FDAADA), 2,2′-bis(trifluoromethyl)-4,4′-bis[4-(4-aminobenzamide)] biphenyl (ABTFMB), and 2,2′-bis(trifluoromethyl)-4,4′-bis[4-(4-amino-3-methyl)benzamide] biphenyl (MABTFMB). The derived FLPI-1 (FDAn-FDAADA), FLPI-2 (FDAn-ABTFMB) and FLPI-3 (FDAn-MABTFMB) resins showed good solubility in the polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO). The solution-processing FDAn-PI films exhibited good optical transmittance over 80.0% at a wavelength of 500 nm (T500), yellow indices (b*) in the range of 1.01–5.20, and haze values lower than 1.0%. In addition, the FDAn-PI films showed low optical retardance with optical retardation (Rth) values in the range of 31.7–390.6 nm. At the same time, the FDAn-PI films exhibited extremely high glass transition temperatures (Tg) over 420 °C according to dynamic mechanical analysis (DMA) tests. The FDAn-PI films showed good dimensional stability at elevated temperatures with linear coefficients of thermal expansion (CTE) in the range of (31.8–45.8) × 10−6/K. [ABSTRACT FROM AUTHOR]

Wholly aromatic polyimide (PI) films with good solution processability, light colors, good optical transparency, high storage modulus, and improved heat resistance were prepared and characterized. For this purpose, a multi-component copolymerization methodology was performed from a fluoro-containing dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), a rigid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), and a fluoro-containing diamine, 2,2′-bis(trifluoromethyl)-4,4′-bis [4-(4-amino-3-methyl)benzamide]biphenyl (MABTFMB). One homopolymer, FPI-1 (6FDA-MABTFMB), and five copolymers, FPI-2~FPI-6, containing the BPDA units from 10 mol% to 50 mol% in the dianhydride moieties, were prepared, respectively. The derived PI resins showed good solubility in the polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). The flexible PI films obtained by the solution casting procedure showed good optical properties with the transmittances higher than 74.0% at the wavelength of 450 nm. The PI films exhibited excellent thermal properties, including 5% weight loss temperatures (T5%) over 510 °C, together with glass transition temperatures (Tg) over 350.0 °C according to the peak temperatures of the loss modulus in dynamical mechanical analysis (DMA) measurements. The FPI-6 film also showed the lowest linear coefficient of thermal expansion (CTE) value of 23.4 × 10−6/K from 50 to 250 °C according to the thermomechanical analysis (TMA) measurements, which was obviously lower than that of FPI-1 (CTE = 30.6 × 10−6/K). [ABSTRACT FROM AUTHOR]