期刊
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
卷 208, 期 1-2, 页码 103-108出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/S1381-1169(03)00514-4
关键词
ROMP of norbornene; methylaluminoxane as catalyst and cocatalyst; cis/trans blocky and stereo-blocky polymers; C-13 NMR
Methylaluminoxane (MAO) alone acts as a weak catalyst for the ring-opening metathesis polymerisation of norbornene, thereby providing good evidence that some transient [Al]double bondCdrop metallacarbenes are formed and propagate the reaction. A novel general mechanism of initiation involving generation of metallacyclopentanes, followed by ring contraction to metallacyclobutanes, is proposed. Methylaluminoxane is also a very effective cocatalyst for Mo and W chlorides, and especially for non-ionic carbonyl compounds of these two metals. Remarkably cis/trans highly stereo-blocky polymers are obtained which for the first time show clear resolution (m/r) on some of the C-13 NMR lines. (C) 2003 Elsevier B.V. All rights reserved.
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