Polymerization of 2-oxazolines was carried out using bifunctional and tetrafunctional initiators. Allyl-type dihalides and xylylene dihalides were used as bifunctional initiators. The allyl-type dihalides employed are l,4-dibromo-2-butene and 3-iodo-2-(iodomethyl)-1-propene and the xylylene dihalides are pxylylene diiodide and p-, m•, and o-xylylene dibromides. The degree of polymerization (DP) of the resulting polymer was very close to the feed ratio of the monomer to initiator. From a kinetic study, it was found that the polymerization using these bifunctional initiators for 2-oxazoline is a "fast initiation-slow propagation system". Electrophilic reactivities of allylic dibromide and allyl bromide were also evaluated by MO calculation to confirm the polymerization system. Tetrakis (bromomethyl)ethylene, an allylic tetrahalide, was used as a tetrafunctional initiator. The DP value of the polymer agreed well with the feed ratio. From NMR and GPC analyses the polymer was of star-shaped structure.

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Propagylic halide type compounds such as propagyl bromide, 1,4-dibromo-2-butyne, and 1,6-dibromo-2,4-hexadiyne, were used for the polymerization of 2-oxazolines. The polymerization initiated by these initiators gave polymers with narrow molecular weight distribution. From kinetic study, the polymerization using these initiators is found to be a relatively fast initiation system.

KEY WORDSIonene / Poly(2-oxazoline) / Multicoupling Reaction/ Living Polymerization / Tertiary Diamine / Aromatic Diamine / Polyelectrolyte / Ionene polymers having ionic groups in the polymer main chain are well known. Among them, polymeric quaternary ammonium salts 3 have been prepared by the reaction of a terti- such as water and amines. 5 Very recently we found that allyl-type dihalides are effective bifunctional initiators for the polymerization of ROZO giving rise to a fast initiation system. 6 In using these initiators, PROZO having two living propagating species at both ends 4 can be readily obtained. This paper deals with the first synthesis of ionene polymers 5 by multicoupling reaction in one-pot between PROZO having two living ends 4 and a tertiary or aromatic diamine. EXPERIMENT AL MaterialsElectrophilic (cationic) ring-opening polymerization3 of 2-alkyl-2-oxazoline (ROZO) is a versatile, convenient method to prepare linear poly(N-acylethylenimines) (PROZ0). 4 The polymerization of ROZO proceeds via living propagating species and the living end reacts quantitatively with various nucleophiles Monomer, 2-methyl-2-oxazoline (MeOZO) was purified by distillation over potassium hydroxide. Other reagents and solvents were purified by distillation or recrystalization. All NJ Br~Br -cN-fCH2CH2N ~NCH2CH21m-1~\ Br-