POLYCYCLOTRIMERIZATION OF DIYNES,A NEW APPROACH TO HYPERBRANCHED POLYPHENYLENES  

作　　者：唐本忠 

机构地区：[1]Department of Chemistry, The Hong Kong University of Science and Technology Clear Water Bay, Kowloon, Hong Kong, China

出　　处：《Chinese Journal of Polymer Science》1999年第4期397-402,共6页高分子科学（英文版）

基　　金：This workw was in part supported by the Earmarked Research Grants of the Hong Kong Research Grants Council(HKUST6062/98P and HKUST6149/97P)

摘　　要：Polycyclotrimerization of diynes was explored as a new route to hyperbranched polymers in this investigation. Polymerization of terminal diynes of 1,8-nonadiyne and 1,9-decadiyne was studied using TaCl5, NbCl5, Mo(CO)(4)(nbd) and [Mo(CO)(3)cp](2) as catalysts (where nbd = 2,5-norbornadiene, cp = cyclopentadiene). A soluble polymer was obtained when the polymerization of 1,9-decadiyne was initiated by TaCl5 at low temperature (0 degrees C). The polymer, however, became partially soluble after purification, possibly due to the postpolymerization-induced crosslinking. NbCl5-catalyzed polymerization of 1,9-bis(trimethylsilyl)- 1,8-nonadiyne gave a completely soluble polymer. Soluble polymers were also obtained from the polymerization of 3,9-dodecadiyne initiated by NbCl5, Mo(CO)(4)(nbd), [Mo(CO)(3)cp](2), PdCl2-ClSiMe3 and Pd/C-ClSiMe3. IR, UV, and NMR spectroscopic analysis revealed that different catalysts gave polymers with different structures, ranging from linear polyenes to hyperbranched polyphenylenes. The polymers absorb UV light at around 250 nm and emit fluorescence at 340 nm when they are excited at 248 nm.Polycyclotrimerization of diynes was explored as a new route to hyperbranched polymers in this investigation. Polymerization of terminal diynes of 1,8-nonadiyne and 1,9-decadiyne was studied using TaCl5, NbCl5, Mo(CO)(4)(nbd) and [Mo(CO)(3)cp](2) as catalysts (where nbd = 2,5-norbornadiene, cp = cyclopentadiene). A soluble polymer was obtained when the polymerization of 1,9-decadiyne was initiated by TaCl5 at low temperature (0 degrees C). The polymer, however, became partially soluble after purification, possibly due to the postpolymerization-induced crosslinking. NbCl5-catalyzed polymerization of 1,9-bis(trimethylsilyl)- 1,8-nonadiyne gave a completely soluble polymer. Soluble polymers were also obtained from the polymerization of 3,9-dodecadiyne initiated by NbCl5, Mo(CO)(4)(nbd), [Mo(CO)(3)cp](2), PdCl2-ClSiMe3 and Pd/C-ClSiMe3. IR, UV, and NMR spectroscopic analysis revealed that different catalysts gave polymers with different structures, ranging from linear polyenes to hyperbranched polyphenylenes. The polymers absorb UV light at around 250 nm and emit fluorescence at 340 nm when they are excited at 248 nm.

关 键 词：polycyclotrimerization DIYNE hyperbranched polymer 

分 类 号：TQ316.3[化学工程—高聚物工业]