主链光学活性ω^-十一烯酸-一氧化碳共聚物的合成与表征  

Synthesis and Characterization of Main Chain Optically Active Copolymer of ω^-Undecylenic Acid with Carbon Monooxide

作　　者：袁建超[1] 张玉华[1] 陈敏东[1] 吕士杰[1] 王冬梅[2] 

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,兰州730000 [2]兰州军区总医院药物分析室,兰州730000

出　　处：《高等学校化学学报》2001年第7期1152-1154,共3页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 99330 5 0

摘　　要：Enantioselective alternating copolymerization of carbon monoxide with ω undecylenic acid was carried out using cationic palladium catalyst modified by 1,4 3,6 dianhydro 2,5 dideoxy 2,5 bis(diphenylphosphino) L iditol (DDPPI). The chiral diphosphine was proved to be effective in the enantioselective copolymerization. The pure poly(1,4 ketone) was obtained by dissolving the copolymer containing spiroketal and 1,4 ketone units in 1,1,1,3,3,3 hexafluoro 2 propanol and reprecipitating with methanol. Optical rotation, elemental analysis, spectra of 1H, 13 C NMR and IR showed that our copolymer was an optically active, isotatic, alternating poly(1,4 ketone) structure. The copolymerization was carried out at 45 ℃ for 20 h. Molecular weight: n=1.1× 10 4 versus polystyrene, w/ n=1.84. Molar optical rotation: 20 589 =+43°(CH 3COOC 2H 5, 5.0 mg/mL). The productivity of the copolymer of ω undecylenic acid with carbon monoxide was 40.6 g copolymer/(g Pd·h).Enantioselective alternating copolymerization of carbon monoxide with ω undecylenic acid was carried out using cationic palladium catalyst modified by 1,4 3,6 dianhydro 2,5 dideoxy 2,5 bis(diphenylphosphino) L iditol (DDPPI). The chiral diphosphine was proved to be effective in the enantioselective copolymerization. The pure poly(1,4 ketone) was obtained by dissolving the copolymer containing spiroketal and 1,4 ketone units in 1,1,1,3,3,3 hexafluoro 2 propanol and reprecipitating with methanol. Optical rotation, elemental analysis, spectra of 1H, 13 C NMR and IR showed that our copolymer was an optically active, isotatic, alternating poly(1,4 ketone) structure. The copolymerization was carried out at 45 ℃ for 20 h. Molecular weight: n=1.1× 10 4 versus polystyrene, w/ n=1.84. Molar optical rotation: 20 589 =+43°(CH 3COOC 2H 5, 5.0 mg/mL). The productivity of the copolymer of ω undecylenic acid with carbon monoxide was 40.6 g copolymer/(g Pd·h).

关 键 词：阳离子钯催化剂 对映体选择性交替共聚 全同共聚物 光学活性 合成 ω-十一烯酸-一氧化碳 

分 类 号：O631.24[理学—高分子化学] O632.52[理学—化学]