New Polymerization Reactions by Masaki Hasegawa (auth.)

By Masaki Hasegawa (auth.)

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In conclusion, the four-center photopolymerization is a novel type of topochemical reaction which is crystal-lattice controlled with respect to the whole set of elementary processes44) including initiation, propagation and crystallization of polymer. In a recent report 57)it has been stated that, according to X-ray diffraction analysis and electron microscopy, the space group of DSP (Pbca) is not maintained but that the polymer phase has space group P21ca and the four-center photopolymerization of DSP occurs along the lines of a heterogeneous solid-state reaction which starts at defect sites within the crystal.

Diazoalkanes . . . . . . . . . . . . . . . Spontaneous Alternating Copolymerizations ............. 3 Mechanism of Maerozwitterion Polymerization . . . . . . . 5 C o v a l e n t I n i t i a t o r s . ~ . " . . . . . . . . . . . R e a c t i v i t y of C o v a l e n t B a s e - M o n o m e r A d d u c t s . . . . . . T h e I n f l u e n c e o f C h e m i c a l l y I n e r t Salts o n t h e P o l y m e r i z a t i o n R a t e T h e R o l e of S o l v e n t in C h a r g e S e p a r a t i o n .

X-ray diffraction diagrams of DSP (x-form, needles), DSP (a-form, plates), P2VB, poly-DSP, and polyP2VB (source: Ref. 8) 10 I I I I I I 20 30 2{) (degree) 40 28 M. Hasegawa Changes in the crystal structure during polymerization have also been pursued by Xray crystallographic techniques 26'44). The results indicate that in all photopolymerizable crystals the molecules are arranged such that the relative positions and orientations of the double bonds are favorable for cyclobutane formation. Further, the principal features of the molecular arrangement in the monomer crystals remain unaltered in the polymer and oligomer crystals.

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