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Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof

A technology of late transition metal and silica, applied in the application field of the catalyst in the gas phase polymerization or copolymerization of ethylene, can solve the problems of high catalyst loading cost, limited industrial application, uncontrollable, etc., and achieve good hydrogen regulation sensitivity performance and copolymerization performance, high ethylene polymerization catalytic activity, good particle morphology

Active Publication Date: 2013-10-30
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although there are many research reports on magnesium chloride compound loaded single-site catalysts (PCT Int.Appl.99 / 21898; US 6455647; J.Mol.Catal.A 2002,188,123; PCT Int.Appl.2004 / 078804) , but the cost of carrier preparation and catalyst loading is high, and the particle shape of the carrier is poor and uncontrollable; although the use of spherical magnesium chloride can ensure that the supported catalyst has a good particle shape, the carrier contains alcohol, water, alkoxy and other components. The preparation of the carrier is complicated, and the above shortcomings limit the industrial application of magnesium chloride-supported single-site catalysts
Chinese patent 200910078595.1 provides a method of spray drying to prepare magnesium chloride carrier, and then the carrier is heated, vacuum dried, etc., and then loaded with a transition metal complex. The preparation method of this carrier is also relatively complicated and is not suitable for industrial production.

Method used

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  • Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof
  • Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof
  • Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0030] 1. Preparation of supported catalyst 2,6-bis[1-(2,6-dimethylphenylimine)ethyl]pyridine ferric dichloride Under nitrogen protection, in a 250mL reactor, add anhydrous magnesium chloride 4.868 g, add 130 mL of refined THF, and keep stirring at a constant temperature of 70°C for 1 hour. Add 7.510 g of TS-610 silica gel replaced by nitrogen into the reactor, keep the temperature at 30° C., and stir for 1 hour. Add 0.1937 g of iron homogeneous catalyst 2,6-bis[1-(2,6-dimethylbenzimine)ethyl]pyridine ferric dichloride, and stir at 30°C for 15 minutes. The stirred mother liquor is spray-dried with a spray drying device, the inlet temperature is set to 182°C, the outlet temperature is 98°C, the pumping speed percentage is 100%, the pump speed percentage is 30%, and the nozzle cleaning frequency is 7 times / min , 8.6219 g of the supported catalyst was obtained, the iron content measured by atomic absorption spectroscopy was 0.25%, the tetrahydrofuran content measured by gas chro...

Embodiment 2

[0034] 1. Preparation of supported catalyst 2,6-bis[1-(2,6-dimethylbenzimine) ethyl]pyridine ferric dichloride

[0035]Under the protection of nitrogen, in a 250mL reactor, add 4.85g of anhydrous magnesium chloride, add 130mL of refined THF, and keep stirring at a constant temperature of 70°C for 1 hour. Add 7.55 g of TS-610 silica gel replaced by nitrogen into the reactor, keep the temperature at 30° C., and stir for 1 hour. Add 0.3812 g of iron homogeneous catalyst 2,6-bis[1-(2,6-dimethylbenzimine)ethyl]pyridine ferric dichloride, and stir at 30°C for 15 minutes. The stirred mother liquor was spray-dried with a spray dryer, the inlet temperature was set to 182°C, the outlet temperature was 98°C, the pump speed percentage was 30%, the nozzle cleaning frequency was 7 times / min, and 8.7325g of supported catalyst was obtained. The iron content measured by absorption spectrum was 0.47%, the tetrahydrofuran content determined by gas chromatography was 29.5%, and the particle size...

Embodiment 3

[0039] 1. Preparation of supported catalyst 2,6-bis[1-(2,6-diisopropylphenylimine)ethyl]pyridine ferric dichloride

[0040] Under the protection of nitrogen, in a 250mL reactor, add 4.8703g of anhydrous magnesium chloride, add 130mL of refined THF, and keep heating and stirring at a constant temperature of 70°C for 1 hour. Add 7.5350 g of TS-610 silica gel replaced by nitrogen into the reactor, keep the temperature at 30° C., and stir for 1 hour. Add 0.2145 g of iron homogeneous catalyst 2,6-bis[1-(2,6-diisopropylphenylimine)ethyl]pyridine ferric dichloride, and stir at 30° C. for 15 minutes. The stirred mother liquor is spray-dried with a spray dryer, the inlet temperature is set to 182°C, the outlet temperature is 98°C, the pumping speed percentage is 100%, the pump speed percentage is 30%, and the nozzle cleaning frequency is 7 times / min. 8.9930 g of the supported catalyst was obtained, the iron content measured by atomic absorption spectroscopy was 0.22%, the tetrahydrofu...

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Abstract

The invention relates to a magnesium chloride / silicon dioxide / tetrahydrofuran loaded late transition metal catalyst and a preparation method and application thereof. The preparation method comprises the following steps of: performing reaction between magnesium chloride and a late transition metal complex in an electron donor tetrahydrofuran compound to prepare a matrix; doping the obtained matrix with nanoscale carbon dioxide carrier particles to obtain a suspended liquid; spray drying the obtained suspended liquid to obtain a solid catalyst compound, wherein the molar ratio of magnesium chloride / silicon dioxide / tetrahydrofuran is 0.1-1:0.1-2:5-20, and the weight percentage of central metal M is 0.01-5% in the loaded late transition metal catalyst. The catalyst used for catalyzing copolymerization reaction between ethylene and advanced alpha-olefin is high in copolymerization activity, and obtained resin powder has good particular shape, is high in stacking density, and can be applied to slurry polymerization or vapor phase polymerization process of ethylene.

Description

technical field [0001] The invention relates to a magnesium chloride / silicon dioxide / tetrahydrofuran loaded post-transition metal catalyst used in ethylene gas phase polymerization or copolymerization process and its preparation, as well as the application of the catalyst in ethylene gas phase polymerization or copolymerization. Background technique [0002] The late transition metal olefin polymerization catalyst refers to a catalytic system composed of coordination compounds of late transition metal nickel, palladium, iron, cobalt, etc. and alkyl aluminum compounds. Late transition metals have long been used in the research of olefin polymerization, but because late transition metals have a strong tendency to eliminate β-H, most late transition metal catalysts are only suitable for the dimerization or oligomerization of olefins. to high molecular weight olefin polymers. People have tried to use late transition metals to catalyze the polymerization of olefins, but they hav...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F10/02C08F4/70C08F4/02
Inventor 何书艳王鹏马建英姜涛王伟众陈开付义曹晨刚赵增辉王立娟邵怀启张丽洋马丽张瑀健关鹏鹏任鹤梁立伟景常荣金毅田炳全
Owner PETROCHINA CO LTD
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