Four novel diamines (9-12) were prepared by a two-step procedure from phosphinated phenols (1-4) that were prepared from acid-fragmentation of four bisphenols, including bisphenol A, 4,4-isopropylidenebis(2,6-dimethylphenol), cis(4-hydroxyphenyl)cyclohexane, and 9,9-bis(4-hydroxyphenyl)fluorene, followed by nucleophilic addition of 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Copolyimides based on (9-12)/4,4-diaminodiphenyl ether (ODA)/dianhydride were prepared. The structure-property relationship on the copolyimides was discussed. Due to the structural similarity, (9)/ODA-based copolyimides were compared with (10)/ODA-based copolyimides, while (11)/ODA-based copolyimides were compared with (12)/ODA-based copolyimides. The dimethyl substitutents cause (10)/ODA-based copolyimides to display higher T-g, modulus, dimensional stability, contact angle, and better solubility than (9)/ODA-based copolyimides. (12)/ODA-based copolyimides that exhibit fluorene moieties display higher T-g and thermal stability, but a lower contact angle and poorer solubility than (11)/ODA-based copolyimides that exhibit cyclohexane moieties. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 390-400