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Thermoplastic polyimide (PI) matrixes, including PI-a (cc-34ODA) and PI-b (ct-34ODA) were prepared via the hot-pressing procedures of the resins derived from the 3,4′-oxydianiline (34ODA) and two alicyclic dianhydrides of 1S,2R,4S,5R-hydrogenated pyromellitic dianhydride (ccHPMDA) and 1R,2S,4S,5R-hydrogenated pyromellitic dianhydride (ctHPMDA), respectively. The resins exhibited thermoplastic features with good formability at higher temperatures. The afforded semi-alicyclic PI sheets exhibited enhanced properties in comparison to commercially available, wholly aromatic thermoplastic PIs, such as PI-ref1, which are derived from 3,3′,4,4′-oxydiphthalic anhydride (ODPA) and 4,4′-oxydianiline (44ODA), as well as PI-ref2, which is based on pyromellitic dianhydride (PMDA) and 4,4′-bis(3-aminophenoxy)biphenyl (mBAPB). In addition, the developed PI sheets exhibited high heat deflection temperatures (HDT) of 267.4 °C for PI-a and 268.6 °C for PI-b. There values were significantly higher when compared with those of PI-ref1 (Ratem® YS20, HDT: 239.0 °C), PI-ref2 (Aurum® PL450C, HDT: 238.0 °C), PI-ref3 (Ultem® 1000, HDT: 206.0 °C), PI-ref4 (Therplim® TO65, HDT: 180.0 °C), and PI-ref5 based on phthalic anhydride-terminated fluorinated PIs (HDT: 215.0 °C). In terms of mechanical properties, the current PI sheets showed superior flexural properties among the polymers with the flexural strength of 189.0 ± 11.7 MPa (PI-a) and 200.5 ± 4.2 MPa (PI-b), respectively. In addition, the PI sheets exhibited comparable compression properties, inferior impact strength, and tensile properties compared with the referenced PI counterparts. Basically, the PI-b sheet showed better comprehensive properties than those of the stereoisomeric PI-a analog. [ABSTRACT FROM AUTHOR]

Optically transparent polyimide (PI) films with good atomic oxygen (AO) resistance have been paid extensive attention as thermal controls, optical substrates for solar cells or other components for low Earth orbit (LEO) space applications. However, for common PI films, it is usually quite difficult to achieve both high optical transparency and AO resistance and maintain the intrinsic thermal stability of the PI films at the same time. In the current work, we aimed to achieve the target by using the copolymerization methodology using the fluorinated dianhydride 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride (6FCDA), the fluorinated diamine 2,2-bis [4-(4-aminophenoxy)phenyl]hexafluoropropane (BDAF) and the polyhedral oligomeric silsesquioxane (POSS)-containing diamine N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) as the starting materials. The fluoro-containing monomers were used to endow the PI films with good optical and thermal properties, while the silicon-containing monomer was used to improve the AO resistance of the afforded PI films. Thus, the 6FCDA-based PI copolymers, including 6FCPI-1, 6FCPI-2 and 6FCPI-3, were prepared using a two-step chemical imidization procedure, respectively. For comparison, the analogous PIs, including 6FPI-1, 6FPI-2 and 6FPI-3, were correspondingly developed according to the same procedure except that 6FCDA was replaced by 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Two referenced PI homopolymers were prepared from BDAF and 6FDA (PI-ref1) and 6FCDA (PI-ref2), respectively. The experimental results indicated that a good balance among thermal stability, optical transparency, and AO resistance was achieved by the 6FCDA-PI films. For example, the 6FCDA-PI films exhibited good thermal stability with glass transition temperatures (Tg) up to 297.3 °C, good optical transparency with an optical transmittance at a wavelength of 450 nm (T450) higher than 62% and good AO resistance with the erosion yield (Ey) as low as 1.7 × 10−25 cm3/atom at an AO irradiation fluence of 5.0 × 1020 atoms/cm2. The developed 6FCDA-PI films might find various applications in aerospace as solar sails, thermal control blankets, optical components and other functional materials. [ABSTRACT FROM AUTHOR]

A series of ester‐ and fluoro‐containing thermoplastic polyimide (PI) films, PEsI‐1 ~ PEsI‐4 have been prepared by the two‐step thermal imidization procedure via the soluble poly(amic acid) (PEsAA) precursors from the copolymerization of four monomers, including the dianhydrides of bisphenol A dibenzoate‐3,3′,4,4′‐tetracarboxylic acid dianhydride (TMBPA) and 3,3′, 4,4′‐biphenyl tetracarboxylic acid dianhydride (BPDA) and the diamine monomers of 4‐aminophenyl‐4′‐ aminobenzoate (APAB) and 2,2′‐bis(trifluoromethyl)‐4,4′‐diamino biphenyl (TFMB) in the polar aprotic solvent of N‐methyl‐2‐pyrrolidinone (NMP). The PI films obtained from the high‐temperature dehydration of the PEsAA solutions exhibited the good thermal stabilities with the glass transition temperatures (Tg) over 269°C, the 5% weight loss temperatures (T5%) higher than 480°C, and the linear coefficients of thermal expansion (CTE) values in the range of 17.7 × 10−6/K–33.6 × 10−6/K in the temperature range of 50–250°C. Meanwhile, the PI films showed good thermoplasticity in the dynamic mechanical analysis (DMA) tests, in which the storage modulus of the PI films dropped sharply in the temperature range of glass transition of the polymers. At last, the PI films exhibited the good dielectric properties with the breakdown voltages (Vb) over 5200 V, the dielectric strength (Ds) higher than 210 V/μm, the dielectric constants (Dk) in the range of 3.26 ~ 3.32 at the frequency of 10 GHz, and the dielectric dissipation factors (Df) of 0.0038 ~ 0.0047. Compared with the commonly used PEsI‐ref film for high‐frequency flexible copper clad laminates (FCCL), the currently developed PI films exhibited the obviously increased Tg values, decreased CTE values, and comparable dielectric properties. [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]