Polyimides Derived from Mellophanic Dianhydride

Abstract

The synthesis of mellophanic dianhydride (MPDA), an isomer of pyromellitic dianhydride (PMDA), was studied. A trend of forming cyclic oligomers in the reactions of MPDA with 4,4‘-oxydianiline (ODA) or 4,4‘-methylenedianiline (MDA) in DMAC was found. The cyclic dimer from MPDA/MDA was isolated and fully characterized, including an X-ray crystallographic analysis. The reactions of MPDA with aromatic diamines were found much more complicated than those of PMDA. A model study was performed to clarify the reactions. Several byproducts were isolated and characterized, so that, in an usual two-step process to prepare polyimides, imide, amide linkage, and carboxylic group may be involved in the polymer structure. The water, either existing in solvent or being generated during the imidization, is the main reason for the side reactions. The properties of some polyimides derived from MPDA and diamines were tested and compared with those of the isomeric polyimides derived from PMDA.

Dynamic tensile properties of a novel Kapton-type asymmetric polyimide derived from 2-phenyl-4,4′-diaminodiphenyl ether

“…6 Meanwhile, amorphous PIs derived from non-planar and asymmetrical diamines have also been reported. Yang et al 8 reported that the PIs derived from PMDA and 3-phenyl-1,4-bis(4-aminophenoxy) benzene (p-TPEQ) showed a higher T g at 286 1C in comparison with bis(4-aminophenoxy)benzene-based PI (T g ¼272 1C). 8 Morikawa et al [9][10][11] also reported the preparation and thermal properties of aromatic PIs derived from a series of phenyl groupsubstituted 4,4¢-ODA derivatives.…”

“…Yang et al 8 reported that the PIs derived from PMDA and 3-phenyl-1,4-bis(4-aminophenoxy) benzene (p-TPEQ) showed a higher T g at 286 1C in comparison with bis(4-aminophenoxy)benzene-based PI (T g ¼272 1C). 8 Morikawa et al [9][10][11] also reported the preparation and thermal properties of aromatic PIs derived from a series of phenyl groupsubstituted 4,4¢-ODA derivatives. Particularly, bis(4-amino-2-biphenyl)ether-based PMDA PI showed significant improvements in solubility in polar aprotic solvents and a higher T g at 303 1C than the aforementioned p-TPEQbased PIs.…”

Novel phenylethynyl-terminated PMDA-type polyimides based on KAPTON backbone structures derived from 2-phenyl-4,4′-diaminodiphenyl ether

“…Yang et al 18,19 reported PIs derived from PMDA and 3-phenyl-1,4-bis(4-aminophenoxy) benzene (p-TPEQ) that showed a higher T g than bis(4-aminophenoxy)-benzene-based PI (T g ¼ 272 1C) at 286 1C. These results show that the pendant phenyl group of p-TPEQ restricts the free rotation of the ether linkage and produces a higher T g because of the expansion of a free rotational unit in the PI chain.…”

Synthesis and properties of polyimides based on isomeric (4, 4′-methylenediphenoxyl) bis (phthalic anhydride)s (BPFDAs)

“…This results in an increase the solubility, a decrease in the complex viscosity, and enhanced T g s due to the rotation-restricted structures [6]. A series of polyimides based on isomeric dianhydrides (such as MPDA, BPDA, BTDA, ODPA, TDPA and HQPDA) have been investigated and the structure-property relationships have been established by different groups [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20].…”