Living carbocationic polymerization. LXII. Living polymerization of styrene, p-methylstyrene and p-chlorostyrene induced by the common ion effect
✍ Scribed by András Nagy; István Majoros; Joseph P. Kennedy
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 232 KB
- Volume
- 35
- Category
- Article
- ISSN
- 0887-624X
No coin nor oath required. For personal study only.
✦ Synopsis
The effect of common anion producing salt, tetrabutylammonium chloride (n-Bu 4 NCl), on the livingness and kinetics of styrene (St), p-chlorostyrene ( pClSt), and p-methylstyrene (pMeSt) polymerization initiated by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl 4 system has been investigated. Uncontrolled (conventional) carbocationic polymerization of St and pMeSt can be converted to living polymerization by the use of n-Bu 4 NCl. Under similar conditions the polymerization of pClSt is living even in the absence of n-Bu 4 NCl, although the molecular weight distribution (MWD) of the polymer becomes narrower in the presence of this salt. The apparent rates of polymerizations decrease in the presence of n-Bu 4 NCl in proportion with the concentration of the salt. The rate of living polymerization of pClSt is noticeably lower than that of St, while that of pMeSt is higher. The apparent rate constants, k A p , of these polymerizations have been determined, and the effects of the electron donating pMe-and electron withdrawing pCl-substituents relative to the rate of St polymerization have been analyzed.