S IMMARY: 9-Allylcarbazole, 9-A2-butenylcarbazole, 9-A*-pentenylcarbazole and 9-As-hexenylcarbazole wkre synthesized and their polymerization with ZIEGLER-NATTA catalyst systems studied. 9-Allylcarbazole could not be polymerized and 9-A3-butenylcarbazole could only be polymerized with extreme difficulty. However, 9-A4-pentylcarbazole and 9-A"hexeny1carbazole could be polymerized a t conversions of about 55 yo. These results are interpreted in terms of steric hindrance about the vinyl group. No evidence of complexing due to the basic nitrogen atom was noted: Of the catalyst systems used only Et,AlCl-yTiCl, was found to be effective in the polymerization. As judged by X-ray diffraction and insolubility the polymers were highly crystalline. ZUSAMMENFASSUNG:9-Allylcarbazol, 9-A3-Butenylcarbazol, 9-A4-Pentenylcarbazol und 9-As-Hexenylcarbazol wurden synthetisiert, und ihre Polymerisation mit ZIEGLER-NATTA-Katalysatorsystemen wurde untersucht. 9-.4llylcarbazol lieB sich nicht polymerisieren, und 9-A3-Butenylcarbazol konnte nur unter groRen Schwierigkeiten polymerisiert werden. Dagegen wurden 9-A4-Pentenylcarbazol und 9-A5-Hexenylcarbazol zu Umsatzen von ca. 55 yo polymerisiert. Die Ergebnisse werden durch sterische Hinderung an der Vinylgruppe erklart. Komplexbildung durch das basische Stickstoffatom wurde nicht beachtet. Von den benutzten Katalysatorsystemen war nur Et,A1C1-yTiC13 polymerisationsaktiv. Aus RoNTGENspektren und Unloslichkeit wurde auf eine hohe Kristallinitat der Polymeren geschlossen.

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Monomers and polymers of 3‐vinyl‐N‐ethylcarbazole, 3‐vinyl‐N‐methylphenothiazine, 3,7‐divinyl‐N‐methylphenothiazine, N‐acrylylcarbazole, N‐acrylylphenothiazine, and N‐acrylyl‐ and N‐methacrylyldibenzazepine have been synthesized. The synthetic procedures for preparing the monomers and polymers are described.

The lowest E* value recorded12JJ for high polymers is that of polydimethylsiloxane, namely, 3.6 or 4.3 kcal./mole. This is in keeping with its highly flexible chain. Among the factors contributing to this chain flexibility are ( a ) lack of substituents on every other chain atom, (6) the greater length of silicon-carbon than of carbon-carbon bonds (1.88 versus 1.54 A.), meaning that the methyl groups of polydimethylsiloxane are farther removed from the backbone than are those of polyisobutylene, for instance, and interfere less with rotation about the bonds in the backbone, ( c ) that silicon-oxygen bonds are longer than carbon-carbon bonds, and that, moreover ( d ) the attraction between silicon-oxygen dipoles is considerably reduced through shielding by the methyl groups.

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