ISSN:
0449-296X
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
1-Vinylcyclohexene (VCH), which has one of the double bonds in the ring and the other outside the ring, was synthesized and polymerized by cationic catalysts. The reactivity of VCH was very large in the polymerizations catalyzed by boron trifluoride etherate (BF3OEt2) and stannic chloride-trichloroacetic acid complex. Similar to other cyclic dienes, the polymerization of VCH was a nonstationary reaction having a very fast initiation step. The polymerization proceeded by either a 1,2- or a 1,4-propagation mode in which vinyl group was always involved. Particularly when BF3OEt2 was used as a catalyst, an intramolecular proton or an intramolecular hydride ion transfer reaction took place, resulting in the formation of methyl groups in the polymer. The degree of polymerization of polymer formed was about 10. This indicates the preponderance of monomer transfer reaction. To investigate the reason for the high reactivity of cyclic dienes, cationic copolymerizations of VCH and 3-methyl-cis/trans-1,3-pentadiene (cis/trans-MPD) was carried out. The relative reactivity of monomers decreased in the order VCH 〉 trans-MPD 〉 cis-MPD. On the other hand, the resonance stabilization of monomers decreased in the order VCH 〉 trans-MPD 〉 cis-MPD. Therefore, it could be considered that the monomer reactivity is mainly determined by the stability of carbonium ion intermediate. The relative stability of carbonium ion must be VCH 〉 trans-MPD 〉 cis-MPD. Thus the influence of the conformation of ion on its stability was clearly demonstrated.
Additional Material:
11 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1971.150091014
