Poly (amic acid) s (PAAs) were synthesized using 4,4′-(hexafluoroisopropyl-idene) diphthalic anhydride (6FDA) and two types of diamines—bis(3-aminophenyl) sulfone (BAS) and bis(3-amino-4-hydroxyphenyl) sulfone (BAS-OH). Two series of transparent polyimide (PI) hybrid films were synthesized by solution intercalation polymerization and thermal imidization using various concentrations (from 0 to 1 wt%) of organically modified clay Cloisite 30B in PAA solution. The thermo-mechanical properties, morphology, and optical transparency of the hybrid films were observed. The transmission electronic microscopy (TEM) results showed that some of the clays were agglomerated, but most of them showed dispersed nanoscale clay. The effects of -OH groups on the properties of the two PI hybrids synthesized using BAS and BAS-OH monomers were compared. The BAS PI hybrids were superior to the BAS-OH PI hybrids in terms of thermal stability and optical transparency, but the BAS-OH PI hybrids exhibited higher glass transition temperatures (Tg) and mechanical properties. Analysis of the thermal properties and tensile strength showed that the highest critical concentration of organoclay was 0.50 wt%.
A series of linear aromatic copolyimides (Co-PIs) were synthesized by reacting 4,4′-biphthalic anhydride (BPA) with various molar contents of 2,2′-bis(trifluoromethyl)benzidine (TFB) and p-xylylenediamine (p-XDA) in N,N′-dimethylacetamide (DMAc). Co-PI films were fabricated by solution casting and thermal imidization with poly(amic acid) (PAA) on glass plates. The thermo-optical properties and gas permeabilities of Co-PI films composed of various molar ratios of p-XDA (0.2–1.0 relative to BPA) were investigated. Thermal properties were observed to deteriorate with increasing p-XDA concentration. However, oxygen-transmission rates (O2TRs) and optical transparencies improved with increasing p-XDA concentration. Co-PI hybrids with a 1:0.2:0.8 molar ratio of BPA:TFB:p-XDA and organically modified hectorite (STN) were prepared by the in situ intercalation method. The morphologies and the thermo-optical and gas permeation properties of the hybrids were examined as functions of STN loading (5–50 wt %). XRD and TEM revealed substantial increases in clay particle agglomeration in the Co-PI hybrid films as the clay loading was increased from 5 to 50 wt %. The coefficient of thermal expansion (CTE) and the O2TR of a Co-PI hybrid film were observed to improve with increasing STN concentration; however, its optical transparency decreased gradually with increasing STN concentration.
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