Chem. J. Chinese Universities ›› 2001, Vol. 22 ›› Issue (7): 1152.

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

YUAN Jian-Chao1, ZHANG Yu-Hua1, CHEN Min-Dong1, LÜ Shi-Jie2   

  1. 1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China;
    2. Department of Drug Analysis, General Hospitalof Lanzhou Military Command, Lanzhou 730000, China
  • Received:2001-02-05 Online:2001-07-24 Published:2001-07-24

Abstract: 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 spiroket al and 1,4-ketone units in1,1,1,3,3,3-hexafluoro-2-propanol and reprecipitating with methanol. Optical rotation, elemental analysis, spectra of 1H NMR, 13C NMRand IRshowed 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: Mn=1.1× 104 versus polystyrene,Mw/Mn=1.84. Molar optical rotation: [α]58920 =+43°(CH3COOC2H5, 5.0 mg/mL). The productivity of the copolymer of ω-undecylenic acid with carbon monoxide was 40.6 g copolymer/(g Pd·h).

Key words: Cationic palladium catalyst, Chiral ligand, Enantioselective alternating copolymerization, Isotactic copolymer, Optical activity

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