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Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum

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Polymerization of methyl methacrylate (MMA) withtert-butyllithium (t-C4H9Li) in toluene in the presence of aluminum alkoxides such as ethoxide,tert-butoxide and 2,6-di-tert-butylphenoxide, were examined at various Al/Li ratios. In the cases of ethoxide andtert-butoxide, predominantly isotactic polymers with broad molecular weight distribution were obtained. Combinations oft-C4H9Li and bis(2,6-ditert-butylphenoxy)methylaluminum [MeAl(ODBP)2] were found to be an efficient initiating system for heterotactic polymerization of MMA, which gives PMMA rich in heterotactic triads up to 68% with narrow molecular weight distribution (Mw/Mn=1.09−1.17). End group analysis by1H NMR indicated thatt-C4H9Li initiates the polymerization and MeAl(ODBP)2 works as a stereospecific modifier. From stereosequence analysis of the heterotactic PMMA by13C NMR, it was found that the calculated pentad fractions from the first-order Markovian statistics (Pm/r=0.742, Pr/m=0.627) fitted the observed ones better than those from Bernoullian statistics. The glass transition temperature of the heterotactic PMMA was 13°C lower than that of syndiotactic PMMA, and the intrinsic viscosity in tetrahydrofuran was close to that of isotactic PMMA with a similar molecular weight but higher than that of syndiotactic PMMA.

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Kitayama, T., Zhang, Y. & Hatada, K. Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum. Polymer Bulletin 32, 439–446 (1994). https://doi.org/10.1007/BF00587886

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  • PMMA
  • Glass Transition Temperature
  • Alkoxide
  • Molecular Weight Distribution
  • Methyl Methacrylate