Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-san...Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a–5c. Complexes 1, 4 and 5a–5c show trans-1,2-regioselectivities and high activities, of which 5c exhibits excellent isoselectivity(mmmm>99%). Conversely, complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4>99%, mm>95%). Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced T_(g)(from-20 ℃ to 79 ℃ and 74 ℃) and hydrophilicity.展开更多
基金financially supported by the open research fund program of Science and Technology on Aerospace Chemical Power Laboratory (No. STACPL120221B03)the National Natural Science Foundation of China (Nos. s22175059,52073275 and U21A20279)。
文摘Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a–5c. Complexes 1, 4 and 5a–5c show trans-1,2-regioselectivities and high activities, of which 5c exhibits excellent isoselectivity(mmmm>99%). Conversely, complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4>99%, mm>95%). Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced T_(g)(from-20 ℃ to 79 ℃ and 74 ℃) and hydrophilicity.
