Catalyst used for olefine polymerization or copolymerization, its preparation method and application

A technology for olefin polymerization and copolymerization, which is used in catalysts for olefin polymerization or copolymerization, preparation and application fields, and can solve problems such as being unsuitable for propylene polymerization and ethylene-propylene copolymers, poor catalyst particle morphology, and insufficient sensitivity to hydrogen conditioning. problem, to achieve the effect of excellent impurity resistance, narrow particle distribution and good particle shape

Active Publication Date: 2006-01-11
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, when the catalyst is used for ethylene polymerization, there are still disadvantages such as poor catalyst particle shape, difficulty in use in a gas-phase fluidized bed, low activity, and insufficient sensitivity to hydrogen adjustment. In addition, olefin copolymerization performance, especially ethylene-propylene copolymerization performance To be further improved
[0004] Patent CN1229092 improved the catalyst preparation method in CN85100997. In the step of dissolving magnesium halide to form a uniform solution, ethanol was added to modify magnesium halide, so that the activity of the prepared catalyst was greatly improved when catalyzing ethylene polymerization, but it was not suitable for propylene Polymerization and production of ethylene-propylene copolymers

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] 1. Preparation of magnesium / titanium solids

[0030] In the reaction kettle that has been repeatedly replaced by high-purity nitrogen, 6.5 kg of anhydrous magnesium chloride, 132.7 liters of toluene, 5.4 liters of epichlorohydrin, and 16.9 liters of tributyl phosphate were added in sequence, at a stirring speed of 130 rpm and a temperature of 60 ° C , reacted for 2.5 hours, added 1.89 kg of phthalic anhydride, continued the reaction for one hour, cooled to -28°C, added 56 liters of titanium tetrachloride dropwise, gradually raised the temperature to 85°C, kept the temperature for one hour, filtered off the mother liquor, and passed the inert The diluent toluene and the organic solvent hexane are washed several times and then dried to obtain the solid A containing magnesium / titanium.

[0031] 3. Preparation of solid titanium catalyst components

[0032] Suspend the above-prepared solid A in toluene, add 1.4 liters of ethanol and 48 liters of titanium tetrachloride at -1...

Embodiment 2

[0038] 1. Preparation of magnesium / titanium solids

[0039] In the reaction kettle that has been repeatedly replaced by high-purity nitrogen, 4.8 grams of anhydrous magnesium chloride, 93 milliliters of toluene, 4.0 milliliters of epichlorohydrin, and 12.5 milliliters of tributyl phosphate were added in sequence, at a stirring speed of 450 rpm and a temperature of 60 ° C , reacted for 2 hours, added 1.4 g of phthalic anhydride, continued to react for one hour, cooled to -28°C, added 56 ml of titanium tetrachloride dropwise, gradually raised the temperature to 85°C, kept at constant temperature for one hour, filtered off the mother liquor, and passed the inert The diluent toluene and the organic solvent hexane are washed several times and then dried to obtain the solid A containing magnesium / titanium.

[0040] 2. Preparation of solid titanium catalyst components

[0041] Suspend the above-prepared solid A in toluene, add 1.7 ml of n-butanol and 48 ml of titanium tetrachloride ...

Embodiment 3

[0047] 1. Preparation of magnesium / titanium solids

[0048] With embodiment 2.

[0049] 2. Preparation of solid titanium catalyst components

[0050] Suspend the above-prepared solid A in toluene, add 3.0 ml of isooctyl alcohol at 10°C, cool down to -10°C, add 48 ml of titanium tetrachloride, gradually raise the temperature to 110°C, add 1.0 ml of DIBP at 80°C, 110 ℃ to temperature after constant temperature for 1 hour, after filtering off the liquid, use 48 milliliters of titanium tetrachloride and 72 milliliters of toluene to keep the temperature at 110 ℃ for 2 hours, repeat the treatment once after filtering, then wash 5 times with hexane, and the remaining solid product Vacuum dried to obtain a solid titanium catalyst component. Wherein the titanium content is 2.34% (wt), the DIBP content is 10.57% (wt), the specific surface area of ​​the catalyst is 273.6m 2 / g, the pore volume is 0.26cm 3 / g, the pore diameter is 3.78nm. .

[0051] 3. Polymerization 1

[0052] Pro...

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Abstract

A catalyst for the polymerization or copdymerization of olefin is composed of Ti-contained solid component A, organoaluminium compound B and organosilicon compound C. Said A is prepared through dissolving magnesium halide in the mixture of organic epoxy compound, organophosphorus compound and inertial diluent, adding educing agent and magnesium halide or its derivatives to educe out Mg/Ti contained deposit, and carrying a surface modifier, a titanium halide or derivative and an electronic doner. It can be used for the polymerization of propene or copolymerization of propene-ethene.

Description

technical field [0001] The present invention relates to a catalyst component for olefin polymerization or copolymerization, its preparation method, and its application in olefin polymerization or copolymerization. Background technique [0002] In the late 1970s, companies such as Mitsui Petrochemical Corporation of Japan and Monai of the United States successfully developed titanium-magnesium high-efficiency carrier catalysts with magnesium chloride as the carrier. Because the carrier was used to improve the utilization rate of the active center of the titanium atom, the catalytic activity was improved. It is much higher than conventional catalysts and simplifies the polymerization process, so the world's polyolefin industry has developed rapidly. Conventional methods for preparing highly active supported catalysts are generally co-grinding, grinding and impregnating, spraying carrier forming and high-speed stirring carrier forming, etc. The main disadvantage of the catalys...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F4/645
Inventor 王志武谭忠郭正阳张凯崔海祥李天益肖军寇鹏严立安徐惠娟王宇
Owner CHINA PETROLEUM & CHEM CORP
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