Alpha-diimine compound, metal complex and load containing compound and application thereof

A technology of diimine compounds and metal complexes, which is applied in the direction of preparation of imino compounds, nickel organic compounds, compounds containing Group 8/9/10/18 elements of the periodic table, etc. Difficult to control the shape of the material, poor thermal stability and other problems

Active Publication Date: 2015-09-23
HEBEI UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

And the support of α-diimine compound metal complex is used as the main catalyst in the polymerization of olefins, which improves the sticky still and polymer morphology in the practical application of homogeneous α-diimine post-transition metal catalysts in the current technology. Difficult to control, large amount of cocatalyst, poor thermal stability, etc., and the covalently bonded loading method prevents the complex from detaching from the carrier

Method used

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  • Alpha-diimine compound, metal complex and load containing compound and application thereof
  • Alpha-diimine compound, metal complex and load containing compound and application thereof
  • Alpha-diimine compound, metal complex and load containing compound and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] 5-[4-(2-Hydroxyethyl)phenoxy]acenaphthenequinone bis(2,6-diisopropyl)phenylimine c1 (that is, the structure of compound C, where Ar=4-ethylphenyl , R 1 =R 2 = (2,6-diisopropyl) phenyl) synthesis:

[0041] Its preparation route is as follows:

[0042]

[0043] Synthesis of 5-[4-(2-hydroxyethyl)phenoxy]acenaphthenequinone b1 (that is, the structure of compound B, wherein Ar=4-ethylphenyl):

[0044] Add 13.1g (50mmol) of 5-bromoacenaphthylquinone in the reaction bottle of 100mL, 20.7g (150mmol) K 2 CO 3 , 50 mL of dry DMF, and start stirring. Add 13.8g (100mmol) a1 during the stirring process, react at 60°C, the reaction is stopped after the chromatographic trace traces that the reactants have completely reacted. The reaction dark brown solution was poured into ice water, and the obtained solid was purified by silica gel chromatography to obtain 15 g of yellow crystals of compound b1 with a yield of 94%. 1 H NMR (400MHz, CDCl 3 ): δ8.62(d, J=8.4Hz, 1H), δ8.16(d,...

Embodiment 2

[0048]5-(4-Hydroxymethylphenoxy) acenaphthoquinone bis (2,6-diisopropyl) phenylimine c2 (that is, the structure of compound C, where Ar = 4-methylphenyl, R 1 = R 2 = (2,6-diisopropyl) phenyl) synthesis:

[0049] Its preparation route is as follows:

[0050]

[0051] Synthesis of 5-(4-hydroxymethylphenoxy)acenaphthenequinone b2 (i.e., the structure of compound B, wherein Ar=4-methylphenyl):

[0052] Add 13.1g (50mmol) of 5-bromoacenaphthenequinone in the reaction bottle of 100mL, 7.45g (60mmol) p-hydroxybenzyl alcohol, 31.84g (150mmol) K 3 PO 4 , 0.47g (2.5mmol) CuI, 0.62g (5mmol) 2-pyridinecarboxylic acid and 50mL dry DMF, heated and stirred at 90°C for 24 hours. Then the dark brown solution of the reaction was poured into a saturated NaCl solution to become a brown suspension, extracted 2-3 times with dichloromethane, and the organic phase was washed with anhydrous MgSO 4 After drying, the solvent was evaporated under reduced pressure to obtain 13 g of brown crystals ...

Embodiment 3

[0055] 5-(4-hydroxyphenoxy)acenaphthenequinone bis(2,6-diisopropyl)phenylimine c3 (i.e., the structure of compound C, where Ar=4-phenyl, R 1 = R 2 = (2,6-diisopropyl) phenyl) synthesis:

[0056] Its preparation route is as follows:

[0057]

[0058] The preparation process of compound b3 is the same as that of compound b1 in Example 1, wherein 5-nitroacenaphthenequinone is used instead of 5-bromoacenaphthenequinone in Example 1; compound a3 is used instead of a1 in Example 1. The preparation process of compound c3 is the same as that of compound c1 in Example 1, wherein compound b3 replaces b1 in Example 1, and the yield of compound c3 is 76%. 1 H NMR (400MHz, CDCl 3 )δ8.24(d, J=8.3Hz, 1H), δ7.37(t, J=7.5Hz, 1H), δ7.29-7.14(m, 8H), δ6.96(d, J=8.9Hz ,2H),δ6.86(d,J=8.9Hz,2H),δ6.65(d,J=7.1Hz,1H),δ3.09-2.98(m,4H),δ1.24-1.21(m ,12H),δ0.99-0.96(m,12H).MS(ESI):m / z 610(M+H + ).

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Abstract

The invention relates to an alpha-diimine compound, a metal complex and a load containing the compound and application thereof. The structural formula of the compound is shown as a formula I. The alpha-diimine compound is provided with a hydroxyl radical on a substituent group connected to an acenaphthene ring, the compound can react with active radicals on a carrier after chemical modification to form covalent bonds, so that the alpha-diimine compound is loaded on the carrier in a covalent bonding manner; and the metal complex containing the alpha-diimine compound, the load containing the alpha-diimine compound and a load of the metal complex containing the alpha-diimine compound can be further obtained. The metal complex containing the alpha-diimine compound and the load containing the metal complex can be used in polymerization of olefins as main catalysts. The metal complex of the load-type alpha-diimine compound can overcome the disadvantages of kettle adhesion, difficult control for polymer conformation, large using amount of catalyst promoter, poor heat stability and the like, and the covalent bonding load manner avoids the complex from being separated from the carrier .

Description

technical field [0001] The present invention relates to the field of olefin catalysis, in particular to an α-diimine compound, a metal complex containing the compound, a load and their application. Background technique [0002] In 1995, Brookhart et al. (J Am Chem Soc, 1995, 117:6414) found that the late transition metal catalyst of α-diimide nickel and palladium catalyzes the polymerization of ethylene into high molecular weight polymers under normal pressure. Subsequent studies have found that the performance of α-diimine catalysts mainly depends on the design of the ligand structure, and the aniline structure is particularly important for the regulation of the catalytic performance (for example, Macromolecules, 2000, 33: 2320, J Am Chem Soc, 2003). , 125: 3068, Acta Catalysis, 2011, 32(3): 490, Macromoleculares, 2009, 42: 7789, Macromol Chem Phys, 2011, 212: 367, Angew Chem Int Ed, 2004, 43: 1821, J Am Chem Soc , 2013, 135:16316; and invention patents WO96 / 23010, US61036...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C251/22C07C249/02C07F15/04C07F15/00C08F110/02C08F110/06C08F110/14C08F132/08C08F112/08C08F232/08C08F210/16C08F4/70
Inventor 杨敏侯彦辉韩伟伟翟飞帆胡博文李琴路晓敏
Owner HEBEI UNIV OF TECH
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