Polymer synthesis by cationic polymerization: Living and functionalized polymers

✍ Scribed by Higashimura, Toshinobu ;Sawamoto, Mitsuo

• Publisher: Wiley (John Wiley & Sons)
• Year: 1985
• Weight: 466 KB
• Volume: 12
• Category: Article
• ISSN: 0025-116X
• DOI: 10.1002/macp.1985.020121985114

✦ Synopsis

Nearly p e r f e c t l i v i n g polymers have been obtained by t h e polymerization of v i n y l e t h e r s (VE) i n i t i a t e d w i t h a mixture of hydrogen iodide and iodine ( H I / 1 2 i n i t ia t o r ) a t low temperature i n nonpolar s o l v e n t s , The polymers had molecular weights d i r e c t l y p r o p o r t i o n a l to monomer conversion and a nearly monodisperse molecular weight d i s t r i b u t i o n (%//Rn c1.1) polymerization took p l a c e by the use of a 1:l adduct between VE and H I (CH3-CHI(OR)) (A) a s an i n i t i a t o r i n conjunction with iodine. From these f a c t s , a new mechanism has been proposed f o r the l i v i n g polymerization i n which the CH-I bond of the i n i t i a l l y formed adduct i s a c t i v a t e d by an e l e c t r o p h i l i c i n t e r a c t i o n of i o d i n e and VE monomer inserts i n t o the a c t i v a t e d CH-I linkage. The r e s u l t a n t polymer again has a CH-I terminal t h a t i s i n t u r n a c t i v a t e d by i o d i n e t o allow f u r t h e r i n s e r t i o n of the monomer. S i m i l a r l y , b i f u n c t i o n a l l i v i n g poly(VE) was obtained with a diiodo compound (CH3CHI-O(~2)-4O-CHI-cH3) , prepared from H I and 1,4-vinyloxybutane, a s an i n i t i a t o r . These mono-and b i f u n c t i o n a l l i v i n g polymers were applied to synthesize AB and ABA block copolymers and functiona l i z e d polyLVE) having terminal and in-chain amino groups.