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Supported alpha-diimine metal complex, and its application in olefin polymerization

A technology of metal complexes and diimine compounds, which is applied in the application field of supported α-diimine metal complexes in olefin polymerization, which can solve the problems of large amount of co-catalyst, difficult control of polymer morphology, poor thermal stability, etc. problem, to achieve the effect of simple and effective loading method, good particle shape and good thermal stability

Inactive Publication Date: 2015-08-12
TIANJIN POLYTECHNIC UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The further object of the present invention is to provide a loading method for the disadvantages of sticking to the kettle, difficult control of polymer morphology, large amount of co-catalyst, and poor thermal stability in the practical application of homogeneous α-diimine post-transition metal catalysts in the current technology. Type α-diimine metal complexes as procatalysts in the polymerization of olefins

Method used

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  • Supported alpha-diimine metal complex, and its application in olefin polymerization
  • Supported alpha-diimine metal complex, and its application in olefin polymerization
  • Supported alpha-diimine metal complex, and its application in olefin polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] 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:

[0042] Its preparation route is as follows:

[0043]

[0044] Synthesis of 5-[4-(2-hydroxyethyl)phenoxy]acenaphthenequinone b1 (that is, the structure of compound B, wherein Ar=4-ethylphenyl):

[0045] 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

[0049] 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:

[0050] Its preparation route is as follows:

[0051]

[0052] Synthesis of 5-(4-hydroxymethylphenoxy)acenaphthenequinone b2 (i.e., the structure of compound B, wherein Ar=4-methylphenyl):

[0053] 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

[0056] 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:

[0057] Its preparation route is as follows:

[0058]

[0059] 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 a supported alpha-diimine metal complex, and its application in olefin polymerization. The structural formula of an alpha-diimine compound in the complex is represented by formula I. The substituent group of the alpha-diimine compound connected to an acenaphthene ring has a hydroxyl group, and the hydroxyl group is connected with a supporter through a hydrogen bond in order to directly support the alpha-diimine compound on the supporter; and a metal complex containing the alpha-diimine compound, a supported substance containing the alpha-diimine compound and a supported substance containing the metal complex containing the alpha-diimine compound can be further prepared. The support mode of the supported alpha-diimine metal complex is simple, and the supported alpha-diimine compound metal complex can be used in olefin polymerization as a main catalyst to overcome the disadvantages of kettle sticking, difficult control of the form of polymers, large use amount of a cocatalyst, poor heat stability and the like.

Description

technical field [0001] The invention relates to the field of olefin catalysis, in particular to the application of a supported α-diimine metal complex in olefin polymerization. Background technique [0002] In 1995, Brookhart et al. (J Am Chem Soc, 1995, 117:6414) found that the late transition metal catalyst of α-diimine nickel and palladium catalyzed the polymerization of ethylene into a high molecular weight polymer under normal pressure. Further studies have subsequently found that the performance of α-diimine catalysts mainly depends on the design of the ligand structure, and the regulation of the aniline structure is particularly important to the catalytic performance (for example, the literature Macromolecules, 2000, 33: 2320, J Am Chem Soc, 2003 ,125:3068, Acta Catalytica Sinica,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, US6103658, C...

Claims

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Application Information

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IPC IPC(8): C07C249/02C07C251/20C07F15/04C07F15/00C08F4/70C08F4/02C08F10/02C08F10/06C08F10/08C08F10/14C08F12/08C08F12/36C08F12/12C08F36/06C08F32/08
Inventor 侯彦辉翟飞帆杨敏韩伟伟胡博文路晓敏李琴
Owner TIANJIN POLYTECHNIC UNIV
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