Fourth subgroup metal complex with rigid annular bridging structure and application of fourth subgroup metal complex
A metal complex, cyclic technology, applied in the direction of 4/14 group organic compounds without C-metal bonds, compounds of periodic table group 4/14 elements, organic chemistry, etc., can solve the problem of low catalytic efficiency, difficult to help Catalyst activation, easy poisoning and deactivation of the active center, etc., to achieve the effect of excellent catalytic performance and good high temperature tolerance
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[0051] The present invention also provides a kind of preparation method of polyolefin, comprises the following steps:
[0052] Copolymerize ethylene and α-olefin in the presence of a catalyst to obtain polyolefin;
[0053] The catalyst includes a main catalyst and a co-catalyst; the main catalyst includes the fourth subgroup metal complex with a rigid ring bridging structure described in the above technical solution.
[0054] In the preparation method provided by the present invention, under the condition of the presence of the catalyst, ethylene and α-olefin are copolymerized in an organic solvent to obtain polyolefin with high molecular weight and high comonomer insertion rate. Wherein, the catalyst is the catalyst for olefin polymerization described above, which will not be repeated here; the α-olefin preferably includes one or more of 1-butene, 1-hexene and 1-octene ; The organic solvent includes but not limited to n-hexane; The concentration of the α-olefin in the organi...
Embodiment 1
[0058] Embodiment 1: the preparation of ligand
[0059] This embodiment is intended to illustrate the preparation process of formula (C) and formula (D) structure ligand:
[0060]
[0061] (1) Taking the structural ligand of formula (C) as an example, combining figure 1 , to describe its detailed preparation process:
[0062] Under nitrogen atmosphere, the 2-R 3 -Bromobenzene (50mmol) was dissolved in 100mL of dry tetrahydrofuran, cooled to -78°C, 55mmol of n-butyllithium was dropped into it, and the reaction was kept at low temperature for 0.5h, and then 60mmol of triisopropyl borate was added dropwise to it, and the low temperature was removed. Rise to room temperature and react for 1 hour, add 5 mL of water to terminate the reaction, add anhydrous magnesium sulfate to it, dry, filter, and rotary evaporate to remove volatile components to obtain the compound of formula I;
[0063] At room temperature, take 2,6-dibromo-4-R 2 - Phenol (100mmol) was dissolved in 400mL of...
Embodiment 2
[0076] Example 2: Preparation of the fourth subgroup metal complex with rigid ring bridging structure
[0077] This example is intended to illustrate the preparation process of metal complexes of the fourth subgroup, specifically including the preparation of metal alkyl complexes (that is, X is an alkyl group in formulas (A) to (B)) and metal halide complexes ( That is, the preparation of X in formula (A)~(B) is halogen):
[0078] (1) Taking metal methide complexes as an example, the detailed preparation process of metal alkylate complexes is described:
[0079] Under a nitrogen atmosphere, dissolve 2 mmol of the ligand in 30 mL of toluene, cool to 0°C, add 2 mmol of n-butyllithium solution dropwise, remove the low temperature, and continue the reaction at room temperature for 1 h. Transfer to MCl previously cooled to -40 °C 4 (2mmol, M=Zr or Hf) in toluene (10mL) suspension, keep the low temperature reaction for 0.5h, slowly rise to room temperature, continue the reaction f...
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