Block copolymerization of alkoxyallenes with phenylallene by the living coordination system with π-allylnickel catalyst:(块共聚的alkoxyallenes phenylalleneπ-allylnickel催化剂由生活协调系统).pdfVIP
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Polymer Bulletin 39,685-692 (1997) Polymer Bulletin
© Springer-Verlag 1997
Block copolymerization of alkoxyallenes with phenylallene
by the living coordination system with r-allylnickel catalyst
Koji Takagi', Ikuyoshi Tomita 2 , Takeshi Endo"
' Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta4259,
Midori-ku, Yokohama 226, Japan
2 Department of Electronic Chemistry, Interdisziplinary Graduate School of Science and En-
gineering, Tokyo Institute of Technology, Nagatsuta 4259, Midori-ku, Yokohama 226, Japan
Received: 8 September 1997/Revised version: 20 October 1997/Accepted: 28 October 1997
Summary
The block copolymerization of alkoxyallenes (2a; n- octyloxyallene and 2b; n-
butoxyallene) with phenylallene (3) was carried out by [(n-allyl)NiOCOCF3]2 (1) in
toluene by the sequential addition of the two monomers. In spite of rather different
polymerizability between 2 and 3 (i.e., 2 has ca. 70 times larger kinetic coefficient than
3), block copolymers having narrow molecular weight distributions were obtained
successfully by controlling the reactivity of the propagating end with the additives such as
triphenylphosphine (PPh3) and copper(I) iodide. In the case of the copolymerization of 3
with 2, the addition of PPh3 was effective for the control of the polymerization step of 2.
The block copolymers with controlled segment length and narrow molecular weight
distributions W n <
(M /M 1.08) were obtained almost quantitatively. Conversely, when the
copolymerization was started from 2, the control of the first stage required PPh3 as a
ligand of the initiator which interrupt the second polymerization of 3. However, block
copolymers with narrow molecular weight distributions (MW <
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