The reaction of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 3,6-dioxaoctane-1,8-diol (triethylene glycol), poly(ethylene oxide)s with Mn = 300,1000 and 3000, or with poly(propylene oxide)s with Mn = 425 and 2000 in excess with AIBN leads to the corresponding bis(hydroxyalkyl) 2,2′-azodiisobutyrates (1a–i). These initiators are suited to synthesize telechelics. With equimolar amounts of AIBN and 3-oxapentane-1,5-diol (diethylene glycol), poly(ethylene oxide)s with Mn = 300, 1000 and 12000, poly(propylene oxide) with Mn = 425, or with poly(tetrahydrofuran) with Mn = 1000 and 2000 polymeric azoinitiators of structure 2 are formed. Blockcopolymers may be synthesized by means of these polym…

Vinylic polymerization of norbornene by Pd(II)-catalysis in the presence of ethylene

Pd(II) catalysts with nitrilo ligands and BF4− counter ions give the best results in vinylic polymerization of norbornene. Absolute molecular weight determination of polynorbornene (PN) by means of light scattering and the three-dimensional shape of PN were also investigated. By correlation of molecular weights Mw with intrinsic viscosity (Staudinger-index) [η], yield a close to 0.5 exponent for the Mark-Houwink equation with solvents chlorobenzene and cyclohexane at 25°C expected for polymer molecules with confined conformation. The vinylic polymerization of norbornene with [(CH3CN)4Pd][BF4]2 (I) in nitromethane in the presence of ethylene results in PN with narrow molecular weight distrib…