An allyl-containing diphenol, 1-(3-allyl-4-hydroxyphenyl)-1-(4-hydoxyphenyl)-1-(6-oxido-6H -dibenz[c,e][1,2]oxaphosphorin-6-yl)ethane (1), was prepared from a one-pot reaction of 9,10-dihydro-oxa-10-phosphaphenanthrene-10oxide, 4-hydroxyacetophenone, and 2-allylphenol in the presence of p-toluenesulfonic acid monohydrate. Then, an allyl-containing dietheramine, 1-(4-(4-aminophenoxy)phenyl)-1-(3-allyl 4-(4-aminophenoxy)-phenyl)-1-(6-oxido-6H-dibenz[c,e][1,2] oxaphosphorin-6-yl)ethane (3), was prepared from the nucleophilic substitution of (1) with 4-fluoronitrobenzene, followed by the reduction of the dinitro groups by Fe/HCl. A flexible polyetheri-mide (PEI) (4) with a curable characteristic was prepared from the condensation of (3) and 4,4 0 -oxydiphthalic anhydride (ODPA) in m-cresol in the presence of isoquinoline. Curing PEI (4) at 300 C leads to PEI (5), which exhibits much a higher T g value (307 C) and a lower coefficient of thermal expansion (CTE) (29 ppm/ C) than PEI (4) (T g ¼ 253 C, CTE 52 ppm/ C).

High‐performance and flexible poly(pyrrolone imide)s (PPyIs) were firstly prepared by the reaction of dianhydrides with an unsymmetric phosphinated triamine, 1‐(3,4‐diaminophenyl)‐1‐(4‐aminophenyl)‐1‐(6‐oxido‐6H ‐dibenz <1,2> oxaphosphorin‐6‐yl)ethane (1), which was prepared by a facile, one‐pot procedure from the reaction DOPO, 4‐aminoacetophenone in excess o‐phenylenediamine in the presence of p‐toluenesulfonic acid. Thermal properties of the resulting PPyIs were evaluated and compared with those of phosphinated polyimides with a similar structure. All of the prepared PPyIs films are tough and creasable. They display higher Tg (374–412 °C), lower coefficient of thermal expansion (34–46 ppm/°C), and better thermal stability (Td 5 wt %: 456–477 °C, 800 °C char yield: 59–63%) than analogous phosphinated polyimides. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2709–2715

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 Tg, modulus, dimensional stability, contact angle, and better solubility than (9)/ODA‐based copolyimides. (12)/ODA‐based copolyimides that exhibit fluorene moieties display higher Tg and thermal stability, but a lower contact angle and poorer solubility than (11)/ODA‐based copolyimides that exhibit cyclohexane moieties. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 390–400