Cationic ring-opening polymerization of oxetane via a non-steady-state controlled polymerization process: A comparison of initiators yielding living and nonliving polymers

被引:23
作者
Bouchekif, Hassen [1 ]
Philbin, Marcia I. [2 ]
Colclough, Eamon [2 ]
Amass, Allan J. [1 ]
机构
[1] Aston Univ, Sch Chem Engn & Appl Chem, Birmingham B4 7ET, W Midlands, England
[2] QinetiQ DERA, Sevenoaks TN14 7BP, Kent, England
关键词
D O I
10.1021/ma062761d
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Our investigations of the cationic ring-opening polymerization of oxetane via active chain end (ACE) mechanism have shown that the use of 1,4-dioxane as solvent can prevent intra- and intermolecular transfer reactions (Scheme 1, part a). Using 3-phenoxypropyl- 1-oxonia-4-oxacyclohexane hexafluoroantimonate as a model of an initiator capable of yielding fast initiation, polymers with predictable number-average molecular weight (up to 160 000 g/mol), narrow molecular weight distribution (1.18 < M-W/M-n,M-GPC < 1.28) were produced with no cyclic oligomer formation. On the basis of the kinetic data, a mechanism of controlled and living polymerization has been proposed in which the rate of mutual conversion between "strain ACE species" (chain terminated by a tertiary 1-oxoniacyclobutane ion, A 1) and "strain free ACE species" (chain terminated by a tertiary 1-dxonia4-oxacyclohexane ion, T1) does not obey a quasi-steady-state assumption but depends on the rate at which the monomer converts the stable species T1 into a living "propagating" center A1(d[A1]/dt = -d[T1]/dt not equal 0). With BF3 center dot CH3OH (i.e., initiator yielding a slow initiation), a drift of the linear dependence MGpc vs conversion to lower molecular weight were observed together with the production of cyclic oligomers, similar to 10% of the monomer consumed in 1,4-dioxane against similar to 30% in dichloromethane.
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页码:1989 / 1995
页数:7
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