Living carbocationic oligomerization of isobutylene by tertiary alcohol/BCl3/1-methyl-2-pyrrolidinone initiating systems. Kinetic study

Citation
C. Rodrigues et al., Living carbocationic oligomerization of isobutylene by tertiary alcohol/BCl3/1-methyl-2-pyrrolidinone initiating systems. Kinetic study, J MACR S PU, A36(1), 1999, pp. 163-182
Citations number
27
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
JOURNAL OF MACROMOLECULAR SCIENCE-PURE AND APPLIED CHEMISTRY
ISSN journal
1060-1325 → ACNP
Volume
A36
Issue
1
Year of publication
1999
Pages
163 - 182
Database
ISI
SICI code
1060-1325(1999)A36:1<163:LCOOIB>2.0.ZU;2-F
Abstract
Low molar mass (<(Mn)over bar>< 4000 g.mol(-1)), narrow molar mass distribu tion (<(Mw)over bar>/<(Mn)over bar> =1.1-1.3) linear alpha-(tert-butyl) ome ga-(tert-chloro) and alpha-cumyl omega-(tert-chloro) oligoisobutylenes (PIB s) were synthesized using two initiating systems: 2,4,4-trimethyl-pentan-2- ol (TMPOH)/BCl3/-40 degrees C and 2-phenylpropan-2-ol (CumOH)/BCl3/-70 degr ees C in the presence of an efficient electron-pair donor (ED), 1-methyl-2- pyrrolidinone (NMP) in methyl chloride. The kinetics of oligomerization wer e investigated. In these two systems, similar polymerization mechanisms wer e observed with, nevertheless, a slight difference of growing species behav ior in the early polymerization steps. The initiation and propagation rate constants were determined; their values are low showing that the addition o f NMP to these initiating systems leads to controlled carbocationic polymer izations. Moreover, the living character of the polymerization was demonstr ated.