New Polymerization Reactions by Masaki Hasegawa (auth.)

By Masaki Hasegawa (auth.)

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I I I I I , ~ . ~ . , ~ 15 20 25 20 (o) 30 35 molecular weigth "as-polymerized" poly-DSP crystal has no definite melting point but depolymerizes to a relatively low molecular weight polymer crystal upon heat treatment. g. poly-p-PDA Me 31). The X-ray diffraction patterns (d) and (e) in Fig. 16 will be discussed in Sect. a. Since two endothermic peaks, exemplified by the poly-DSP crystal in Fig. 1464) are generally observed for the as-prepared polymer crystals and since a weaker peak appears at the lower temperature which grows at the later stage of photopolymerization as shown in Fig.

Recrystallized N > 380 n m ~ Solution ~ Poly-DSP xx340 nm N t 340 nm n3d m0~ n ~ ' - - ~ Solution ~ I )~ 300 nm I I I I Crystal. recrystallized 340 nm" - > 400 nm Crystal. - - - "-z3- Solution _ Amorphous (photooxidative) in air) / Monomer Crystal Lattice Controlled Photopolymerization 340 nm Crystal. ~ ~ ..... "- Cr staL as-polymerized (photostable) as-polymerized Polymer Crystal. Lattice Controlled Thermal Depolymerization The reaction paths in solution are interpreted mostly by well-known reversible reactions between two olefins and a cyclobutane ring.

E. topochemical dimer formation in the regular lattice and subsequent random cycloaddition in a disordered crystal lattice, is presumed for m-PDA Me. V. Changes of Morphology and Thermodiagram in the Course of Polymerization It is of great interest to investigate the continuous changes of morphology and thermodiagram in the course of direct rearrangement of monomer crystals to polymer crystals and to correlate these changes in terms of crystallographic data. Morphological changes, which are classified into four groups, have been correlated to the degree of topotactic control.

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