COPOLYMERIZATION OF CARBON-MONOXIDE AND NORBORNENE DERIVATIVES WITH ESTER GROUPS BY PALLADIUM CATALYST

In this article we will discuss the synthesis of the new copolymers of norbornene derivatives with an eater group and carbon monoxide, using Pd(CH3CN)(4)(BF4)(2) as a catalyst and 2,2'-bipyridine as a ligand in nitromethane/methanol at 60 degrees C. Elementary analysis, infrared spectra, and NMR spectra indicated that copolymers contain ketone, eat er, and bicyclic structures. Methanol functions as the coinitiator and chain transfer agent in copolymerization. A decrease in the molar rat io of [CH3OH]/[Pd] caused an increase in molecular weight and a decrea se in yield of the copolymer. The number-average molecular weight of c opolymers ((M) over bar(n)) ranged from 3800 to 5300, and the glass tr ansition temperature (T-g) ranged from -32 to 117 degrees C. Thermal a nalysis revealed that both T-d(10%) and T-d(max) exceeded 180 and 230 degrees C, respectively. Linear long-chain substituents such as n-C11H 23C(O)-O-CH2-drastically reduced T-g to a value of -32 degrees C. In g eneral, copolymers having a longer linear side-chain substituents of e ater on norbornene have a more desirable solubility. Moreover, X-ray d iffraction demonstrated that the degree of crystallinity decreases wit h an increasing length of side chain substituents. (C) 1998 John Wiley & Sons, Inc.