Highly Organosoluble Polyimides with Pendent Cyclododecane Group: Synthesis and Characterization

Abstract

A new bis(ether anhydride), 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl] cyclododecane dianhydride (BDPCD), was prepared in three steps starting from nitrodisplacement of 4-nitrophthalonitrile with 2,2-bis(4-hydroxyphenyl) cyclododecane (BHPC), followed by alkaline hydrolysis of the dehydration of the resulting bis(ether diacid) (BCPPC) and subsequent dehydration of the resulting bis(ether diacid) (BAPPC). A series of new highly soluble poly(ether imide)s having tert-butyl substitutents, together with noncoplanar and pendent cardo groups were prepared from such bis(ether anhydride) (BDPCD) with various diamines by a conventional two-stage synthesis including the polyaddition and chemical cyclodehydration. The resulting poly(ether imide)s had inherent viscosities inthe range of 0.50-.0.86 dL.g -1 . The GPC measurement revealed that the polymers exhibited number-average and weight-average molecular weight up to 63 000 and 115 000, respectively. All the polymers showed typical amorphous diffraction patterns. All of the poly(ether imide)s showed excellent solubility and were readily dissolved in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), pyridine, cyclohexanone and tetrahydrofuran. Most of the polymers could be dissolved in chloroform as high as 30wt.-% concentration. These polymers had glass transition temperatures (T g ) in the range of 230-262°C. Thermogravimetric analysis (TGA) showed that all polymers were stable, with 10% weights loss recorded above 434°C and 407°C in nitrogen and air, respectively. These transparent, tough and flexible polymer films could be obtained by solution casting from the DMAc solution. These polymer films had tensile strengths in the range of 80-102 MPa and tensile moduli in the range of 1.7-2.0 GPa.