ISSN:
0360-6376
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The proposition that BCl3-coinitiated olefin (isobutylene, styrene) polymerizations terminate by chlorination has been corroborated by model experiments. Key experiments showed that under simulated polymerization conditions neither tert-butyl chloride nor 2-chloro-2,4,4-trimethylpentane reacts with BCl3; that H2O/BCl3 + 2,4,4-trimethyl-1-pentene (TMP) produce 2-chloro-2,4,4-trimethylpentane; and that H2O/BCl3 + isobutylene gives rise to tert-butyl chloride. Extended model studies demonstrated that certain alkyl and benzyl chlorides produce carbenium ions in the presence of BCl3 and that TMP can readily be alkenylated by using 1-substituted allyl chlorides in conjunction with BCl3. These experiments led to the discovery that olefin polymerizations may be initiated by suitable allyl or benzyl chlorides and BCl3. Accordingly, polymerizations of isobutylene have been carried out with RCl/BCl3, where R is allyl or benzyl. These experiments suggest that both controlled initiation and termination, i.e., initiation by alkenylation and termination by chlorination, can be achieved with the allyl chloride/BCl3 initiator system opening new avenues toward the synthesis of asymmetric telechelic polymers.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1977.170151205
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