Abstract
Perdeuterated methyl methacrylate (MMA-d8) was polymerized by C4H9Li in THF at −78°C, and the resultant polymer and oligomer were analyzed for the initiator fragment by 1H NMR spectroscopy. The structure of the oligomer was also studied by mass spectroscopy. The results indicated that the oligomer obtained had two butyl groups. One of them was attached to the initiating chain end and the other was incorporated as a butyl carbonyl group of the butyl isopropenyl ketone unit situated at the terminated chain end. The ketone was formed by an attack of C4H9Li on the carbonyl double bond of the monomer. The polymer contained 3—4 ketone units incorporated into the chain through copolymerization of the butyl isopropenyl ketone with MMA, while the polymer formed in toluene was found to have one ketone unit near the beginning of the chain. Analysis of the polymerization products of MMA-d8 with C4H9Li in THF terminated with methanol-d4 showed that a part of the polymer and oligomer anions abstracted the α-methylene protons of butyl carbonyl group (–CO–CH2–CH2CH2CH3) of the ketone unit during the polymerization. The mechanism of polymerization is discussed in detail on the basis of these results.
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Hatada, K., Kitayama, T., Okahata, S. et al. Studies on the Mechanism of Polymerization of Methyl Methacrylate in Tetrahydrofuran with Butyllithium at −78°C by Using Perdeuterated Monomer. Polym J 13, 1045–1054 (1981). https://doi.org/10.1295/polymj.13.1045
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DOI: https://doi.org/10.1295/polymj.13.1045
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