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Alpha-diimine and metal application of supporting substance of metal complex thereof in olefin polymerization

A technology of metal complexes and diimine compounds, applied in the field of olefin catalysis, can solve the problems of large amount of co-catalyst, difficult to control polymer form, poor thermal stability, etc., and achieves good particle shape, reduced impact, and good thermal stability. Effect

Inactive Publication Date: 2018-09-14
TIANJIN POLYTECHNIC UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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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  • Alpha-diimine and metal application of supporting substance of metal complex thereof in olefin polymerization
  • Alpha-diimine and metal application of supporting substance of metal complex thereof in olefin polymerization
  • Alpha-diimine and metal application of supporting substance of metal complex thereof in olefin polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] 5,6-bis(4-hydroxymethylphenyl)acenaphthenequinone bis(2,6-diisopropyl)phenylimine b1 (that is, the structure of compound B, wherein Ar=p-methylphenyl, R= Synthesis of (2,6-diisopropyl)phenyl, X=hydroxyl):

[0041] Its preparation route is as follows:

[0042]

[0043] Synthesis of 5,6-dibromoacenaphthoquinone bis(2,6-diisopropyl)phenylimine a1:

[0044] Add 5,6-dibromoacenaphthenequinone (2.72g, 8mmol), 2,6-diisopropylaniline (3.36g, 19mmol) and 150mL of anhydrous methanol to a 250mL reaction flask, and add 10 drops With anhydrous formic acid, the mixture was refluxed for 48 hours. The reaction was tracked by chromatography until the reaction of the raw materials was complete. After the reaction mixture was cooled, a brown-red solid was obtained by suction filtration. The solid was purified by silica gel chromatography to obtain 4.69 g of a yellow solid a1 with a yield of 89%. 1 H NMR (400MHz, CDCl 3 ): δ7.79(d, J=7.8Hz, 2H), 7.32-7.29(m, 6H), 6.45(d, J=7.8Hz, 2H...

Embodiment 2

[0048] 5,6-two (4-hydroxyl phenyl) acenaphthene quinone bis (2,6-diisopropyl) phenylimine b2 (i.e. the structure of compound B, wherein Ar = p-phenyl, R = (2, Synthesis of 6-diisopropyl)phenyl, X=hydroxyl):

[0049] Its preparation route is as follows:

[0050]

[0051] Compound a1 (2.63g, 4mmol), 4-hydroxyphenylboronic acid (1.24g, 9mmol), tetrakis(triphenylphosphine) palladium (0.46g, 0.4mmol), anhydrous potassium carbonate (3.73g, 27mmol), 100mL Add toluene and 50mL water into the two-necked flask, and replace the atmosphere in the reaction flask with N 2 , heated to reflux for 10 h, cooled to room temperature, extracted with dichloromethane, dried the organic phase with anhydrous sodium sulfate, filtered and suspended to dryness, and finally separated and purified by column chromatography to obtain 2.6 g of yellow solid b2 with a yield of 95%. 1 H NMR (400MHz, CDCl 3 ): δ7.32-7.29(m, 8H), 6.78-6.75(m, 6H), 6.46(d, J=8.3Hz, 4H), 3.15-3.04(m, 4H), 1.29(d, J=6.8 Hz, 12...

Embodiment 3

[0053] 5,6-two (4-aminophenyl) acenaphthene quinone bis (2,6-diisopropyl) phenylimine b3 (that is, the structure of compound B, wherein Ar = p-phenyl, R = (2, Synthesis of 6-diisopropyl)phenyl, X=amino):

[0054] Its preparation route is as follows:

[0055]

[0056] Compound a1 (2.63g, 4mmol), 4-aminophenylboronic acid (1.23g, 9mmol), tetrakis(triphenylphosphine) palladium (0.46g, 0.4mmol), anhydrous potassium carbonate (3.73g, 27mmol), 100mL Add tetrahydrofuran and 50mL water into the two-necked flask, and replace the atmosphere in the reaction flask with N 2 , heated to reflux for 10h, cooled to room temperature, extracted with dichloromethane, dried the organic phase with anhydrous sodium sulfate, filtered and spin-dried, and finally separated and purified by column chromatography to obtain 2.54g of yellow solid b3, yield 93% . 1 HNMR (400MHz, CDCl 3 ): δ7.29-7.26(m, 8H), 6.70(d, J=8.2Hz, 6H), 6.29(d, J=8.2Hz, 4H), 3.16-3.02(m, 4H), 1.26(d, J=6.7Hz, 12H), 1.03 (d, ...

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Abstract

The invention provides alpha-diimine and metal application of supporting substance of a metal complex thereof in olefin polymerization. The alpha-diimine compound is characterized in that an acenaphthene ring contains two hydroxide radicals or amido which can react with chemically modified active radicals on a supporter to form two covalent bonds, and thus the alpha-diimine compound can be firmlysupported to the supporter in a covalent bond linking manner; thus the supporting substance of the metal complex containing the alpha-diimine compound can be further obtained. The loaded alpha-diimineand the metal complex thereof can be used as main catalysts used in olefin polymerization; the metal compound of the supporting type alpha-diimine complex is capable of overcoming the defects such askettle adhering, difficult control of form of a polymer, a large number of assistant catalysts and low thermal stability; moreover, the complex is prevented from separating from the supporter throughthe covalent bond linking type loading mode.

Description

technical field [0001] The invention relates to the field of olefin catalysis, in particular to the application of an α-diimine and a metal complex support 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. Then people further research found that the performance of α-diimine catalyst mainly depends on the design of the ligand structure, wherein the regulation of the aniline structure to the catalytic performance is particularly important (for example, literature Macromolecules, 2000, 33: 2320, J Am Chem Soc, 2003 J Am Chem Soc , 2013, 135:16316; and invention patents WO96 / 23010, US6103658, CN201010177711.8, CN201210051457.6, CN201210276331.9, CN201010572741.9). [0003] If the α-diimine complex is used in slurry olefin polymerizatio...

Claims

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Application Information

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IPC IPC(8): C08F4/70C08F4/02C08F10/02C08F10/06
CPCC08F4/025C08F4/70C08F10/02C08F10/06
Inventor 侯彦辉孟浩杨敏任合刚韦德帅路小敏崔咪咪
Owner TIANJIN POLYTECHNIC UNIV
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