Abstract
Comprehensive SummaryCoordination polymerization of renewable (E)‐4,8‐dimethyl‐1,3,7‐nonatriene (DMNT) has been performed using pyridyl‐methylene‐ fluorenyl scandium complex 1, half‐sandwich scandium complex 2, diiminophosphinato rare‐earth metal complexes 3a—3c and 4a—4b, bis(phosphino)carbazolide yttrium complex 5 and β‐diketiminato yttrium complex 6. Fluorenyl scandium complexes 1 and 2, activated by [Ph3C][B(C6F5)4] and AliBu3, are moderately active and show perfect 1,2‐regioselective (1,2 > 99%). Conversely, asymmetric diiminophophinato complexes 3a—3c promote the DMNT polymerization to produce high trans‐1,4 regulated products with the activity trend: Sc < Lu < Y. Complexes 4—6 are virtually inactive for the DMNT polymerization although they are highly active in isoprene polymerization. A diblock copolymer bearing 3,4‐polyisoprene block and trans‐1,4‐poly(DMNT) block is obtained using complex 3c in one‐pot reaction. Hydrogenation of trans‐1,4‐poly(DMNT) affords an elastomer with a Tg of –10°C. The epoxidation reaction of trans‐1,4‐poly(DMNT) with 3‐chloroperbenzoic acid transfers the pendant double bonds in the cis configuration into the epoxy groups.
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