A bridged dinuclear metallocene compound and its preparation method and application
A metallocene compound and compound technology, applied in metallocene, hydrocarbon, hydrocarbon and other directions, can solve the problem of molecular weight reduction, and achieve the effect of high syndiotacticity, less co-catalyst and high catalytic activity
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Embodiment 1
[0066] Ligand L1[(CH 3 ) 2 C(C 5 h 4 )(C 13 h 9 )] 2 (CH 2 ) 2 Synthesis
[0067] Ligand L1[(CH 3 ) 2 C(C 5 h 4 )(C 13 h 9 )] 2 (CH 2 ) 2 The synthetic route is as follows:
[0068]
[0069] Add the THF (40mL) solution of 1,2-dichloroethane (24mL, 303.6mmol) dropwise to the THF solution of CpNa (4.048mol / L) under the ice-water bath, a white precipitate gradually appeared, and the addition was completed in half an hour. Rise naturally to room temperature and react overnight; add saturated NaCl to hydrolyze, and a white precipitate appears at the bottom of the bottle. Take the upper layer of yellow clear liquid, adjust the pH to neutral with acetic acid, separate the layers, take the organic phase, and wash the water phase three times with anhydrous ether ( 20mL×3), the organic phases were combined, washed with saturated brine, anhydrous MgSO 4 Dry and distill under reduced pressure to obtain 18 g of ethylene bridge linked dicyclopentadiene, a colorless tra...
Embodiment 2
[0077] Ligand L2[(CH 3 ) 2 C(C 5 h 4 )(C 13 h 9 )] 2 (CH 2 ) 4 Synthesis
[0078] Same as Example 1, 1,4-dichlorobutane replaces 1,2-dichloroethane to prepare bridged fulvene
[0079] Under ice bath, bridged fulvene (10.172g, 29.4mmol) was added dropwise to a solution of FluLi (10.17g, 58.8mmol) in ether (250mL), and a little precipitate formed. After one day of reaction, there was still a small amount of precipitate, hydrolysis, acetic acid Adjust the pH to neutral, separate the liquids, take the organic phase, extract the aqueous phase with ether twice, combine the organic phases, wash with saturated brine, dry with anhydrous magnesium sulfate for 6 hours, filter, and spin off the solvent in vacuo, using petroleum ether as the mobile phase, After separation by column chromatography and concentration, 6.97 g of mucus was obtained with a yield of 35%, which was Ligand L.
[0080] Complex 2[(CH 3 ) 2 C(C 5 h 3 )(C 13 h 8 )ZrCl 2 ] 2 (CH 2 ) 4 Synthesis
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Embodiment 3
[0085] Ligand L3[(CH 3 )(CH 2 CH 3 )C(C 5 h 4 )(C 13 h 9 )] 2 (CH 2 ) 2 Synthesis
[0086] Under an ice bath, ethylene bridge fulvene (7.82g, 29.4mmol) was added dropwise to a solution of FluLi (10.17g, 58.8mmol) in ether (250mL), a little precipitate formed, and after one day of reaction, there was still a small amount of precipitate, which was hydrolyzed. , adjust the pH to neutral with acetic acid, separate the liquids, take the organic phase, extract the aqueous phase with ether twice, combine the organic phases, wash with saturated brine, dry over anhydrous magnesium sulfate for 6 hours, filter, spin off the solvent in vacuo, and use petroleum ether as the mobile The phase was separated by column chromatography, and 6.51 g of mucus was obtained after concentration, with a yield of 37%, which was ligand L.
[0087] Complex 3[(CH 3 )(CH 2 CH 3 )C(C 5 h 3 )(C 13 h 8 )ZrCl 2 ] 2 (CH 2 ) 2 Synthesis
[0088] Under ice-water bath conditions, n BuLi (8mmol...
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