Preparation and properties of semi-alicyclic thermoplastic polyimide sheets with improved optical properties and good mechanical properties from stereoisomeric hydrogenated pyromellitic dianhydrides and fluorinated diamine

Abstract

Abstract Two semi-alicyclic thermoplastic polyimides (PI) have been prepared from stereoisomeric hydrogenated pyromellitic dianhydrides, including 1S,2R,4S,5R-hydrogenated pyromellitic dianhydride (ccHPMDA or H-PMDA) and 1R,2S,4S,5R-hydrogenated pyromellitic dianhydride (ctHPMDA or Hʹʹ-PMDA) and a fluorine-containing diamine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BDAF), respectively. The derived PI-1 (ccHPMDA-BDAF) and PI-2 (ctHPMDA-BDAF) resins were easily soluble in polar aprotic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc) and meanwhile they also exhibited good thermoplasticities. Thus, the PI films (thickness: ~25 µm) and sheets (thickness: ~3 mm) were separately prepared from the PI solutions in DMAc and the PI powders, respectively. The stereoisomeric effects in the ccHPMDA-derived PI-1 and the ct-HPMDA-derived PI-2 apparently affected the melt-flowability of the polymers. PI-2 exhibited lower melting viscosities than that of the PI-1 counterpart. The PI sheets exhibited obviously reduced optical transparency compared with those of the PI films; however better optical transparency than those of the common thermoplastic PI sheets. For example, PI-2 sheet showed the optical transmittance value at the wavelength of 760 nm (T760) of 69.6%, which was 19.5% lower than that of the analogous PI-2 film (T760 = 89.1%), however 50.3% and 65.7% higher than those of the commercially available PI-ref1 sheet (T760 = 19.3%) derived from 3,3ʹ,4,4ʹ-oxydiphthalic dianhydride (ODPA) and 4,4ʹ-oxydianiline (ODA) and the PI-ref2 sheet (T760 = 3.9%, Aurum® PL450C, Mitsui Chem. Co, Ltd., Japan), respectively. Meanwhile, the PI-1 and PI-2 sheets showed the heat deflection temperatures (HDT) of 261.0 oC and 265.0 oC, respectively, which were obviously higher than those of the referenced PIs. At last, the PI sheets exhibited good mechanical properties, including high flexural strength (130.0 ~ 132.0 MPa), flexural modulus (2.87 ~ 2.96 GPa), compression strength (124.4 ~ 149.3 MPa), compression modulus (1.49 ~ 1.59 GPa), and impact strength (129.0 ~ 139.6 KJ/m2).