Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Optically Active Polymers. III. Polymers of 1,3-Dimethylbutyl Methacrylate
Minoru ImotoYoshiyuki Kumata
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1965 Volume 38 Issue 10 Pages 1615-1620

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Abstract

The polymerization of (+)-1,3-dimethylbutyl methacrylate and its optically impure (−)-isomer have been carried out through different three initiations:
(1) n-BuLi in toluene at −78°C gave isotactic polymers (DI and LI). (2) Azobisisobutyronitrile at 60°C gave atactic polymers (DA and LA). (3) Photopolymerization in the presence of azobisisobutyronitrile at −35–−50°C gave syndiotactic polymers (DS and LS). The tacticities of the resulting polymers have been deduced from their softening temperatures and their infrared spectra. Optically active polymers have been fractionated from a benzene solution by adding methanol. In the cases of DI and DA, the specific rotation [α]D increased with the molecular weight, while in the cases of DS, LS and LA, [α]D remained constant during the change in molecular weight. The optical rotatory dispersion of the polymers has been measured. Drude’s equation does not hold. In the case of DA, however, a straight line was obtained by Moffitt’s equation, giving −64.3 as the b-values.

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