142 Advances in Polymer Science Editorial Board: A. Abe. A.-C ...

Poly(macromonomers), Homo- and Copolymerization 139
3.3
Polyacrylates
1,3-Pentadienyl-terminated poly(methyl methacrylate) (PMMA) as well as PSt,
12, have been prepared by radical polymerization via addition-fragmentation
chain transfer mechanism, and radically copolymerized with St and MMA, respectively,
to give PSt-g-PMMA and PMMA-g-PSt [17, 18]. Metal-free anionic
polymerization of tert-butyl acrylate (TBA) initiated with a carbanion from diethyl
2-vinyloxyethylmalonate produced vinyl ether-functionalized PTBA macromonomer,
13 [19].
(12)
(13)
Highly stereoregular PMMA macromonomers, 14, prepared by Hatada and
coworkers, have recently been fractionated by supercritical fluid chromatography
into completely uniform fractions with no structural distribution [20, 21].
They have been oligomerized with a radical (AIBN) or an anionic initiator (3,3dimethyl-1,1-diphenylbutyllithium).
After a new fractionation by SEC comb or
star polymers of completely uniform architecture are obtained. No doubt, these
samples will be most promising to investigate the branched structure-property
relationship.
3.4
Poly(ethylene oxide)
(14)
Norbornenyl-ended macromonomers from poly(ethylene oxide) (PEO), 15, as
well as from PEO-b-PSt or PSt-b-PEO block copolymers, 16a, 16b, have been
prepared by the initiation or termination method of living anionic polymerization
[22, 23]. The ROMP of 16 afforded various types of controlled, core-shell