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Magnesium halide adduct and its application and catalyst component and catalyst system for olefin polymerization and its application and olefin polymerization process

A technology of olefin polymerization and magnesium halide, which is applied in the direction of magnesium organic compounds, can solve the problems of low polymerization activity, poor sensitivity to hydrogen adjustment, and catalysts that need to be further improved, and achieve high polymerization activity, good stereospecific ability, and high industrial application value effect

Active Publication Date: 2019-03-22
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] CN1169840C and CN1286863C disclose a kind of " magnesium chloride-alcohol-phthalate " spherical magnesium chloride adduct, but, the catalyst that forms with this adduct and titanium tetrachloride reaction is low in the polymerization activity when being used for propylene polymerization And the sensitivity of hydrogen adjustment is poor
[0012] CN102796127A discloses a kind of formula is MgXY-mEtOH-n (LB 1 )-k(LB 2 )-p(LB 3 ), wherein X is chlorine or bromine, and Y is chlorine, bromine, C 1 -C 14 Straight chain or branched chain alkyl, C 6 -C 14 Substituted or unsubstituted aryl, C 1 -C 14 straight-chain or branched-chain alkoxy and C 6 -C 14 One of the substituted or unsubstituted aryloxy groups, LB 1 , LB 2 and LB 3 Each is one of carboxylic acid, aldehyde, ether, ester, ketone, silane, amine, nitrile, phenol and alcohol other than ethanol, m is 1-5, n is 0.005-2, k is 0.0005-0.3, p is 0.0005-0.3, the catalyst further prepared by reacting the adduct with titanium halide and an optional internal electron donor can obtain a better balance between hydrogen tuning ability and stereospecific ability, but the polymerization activity of the catalyst still needs to be further improved

Method used

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  • Magnesium halide adduct and its application and catalyst component and catalyst system for olefin polymerization and its application and olefin polymerization process
  • Magnesium halide adduct and its application and catalyst component and catalyst system for olefin polymerization and its application and olefin polymerization process
  • Magnesium halide adduct and its application and catalyst component and catalyst system for olefin polymerization and its application and olefin polymerization process

Examples

Experimental program
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Effect test

Embodiment 1

[0189] (1) In a 500mL reactor, add 150mL white oil (commercially purchased from Guangzhou Mingen Petrochemical Co., Ltd., by weight, water content is lower than 50ppm), 30g magnesium chloride containing 0.44wt% moisture (commercially purchased from Fushun City Xinyi Titanium Factory), 50mL of absolute ethanol (commercially purchased from Beijing Chemical Plant, with a water content of less than 100ppm by weight) and 1mL of 2-methoxybenzoyl chloride (commercially purchased from TOKYO KASEI KOGYO CO. LTD), heated to 120°C with stirring. After 2 hours of constant temperature reaction, the mixture was pressed into 300 mL of methyl silicone oil (commercially purchased from Dow Corning, with a viscosity of 300 centipoise / 20° C., and a water content of less than 50 ppm by weight) preheated to 120 ° C. Stir for 30 minutes at a speed of 1 / min for emulsification. Then, the emulsified product was injected into 2L of hexane (by weight, water content less than 5ppm) pre-cooled to -30° C. ...

Embodiment 2

[0207] (1) Prepare spherical magnesium halide adducts in the same manner as in step (1) of Example 1. The difference is that the magnesium chloride used is magnesium chloride containing 0.65 wt% moisture, and the composition of the prepared magnesium halide adducts is shown in the table 1 listed.

[0208] The magnesium halide adduct was subjected to DSC analysis. In the obtained DSC graph, a melting peak appeared at 97.6° C. and 112.1° C. respectively, and the melting enthalpy value associated with the highest melting peak was 177.3 J / g.

[0209] The X-ray diffraction spectrum of this magnesium halide adduct shows, in the scope of the 2θ diffraction angle of 5-15 °, show to exist in 6.06 ° (14), 8.82 ° (100), 8.98 ° (50), 9.74 ° ( 66), 5 diffraction lines under the diffraction angle 2θ of 11.48°(11); the values ​​in brackets represent the intensity I / I relative to the strongest diffraction line 0 .

[0210] (2) The spherical catalyst component was prepared in the same manner...

Embodiment 3

[0219] (1) In a 500mL reaction kettle, add 150mL of white oil (commercially purchased from Guangzhou Mingen Petrochemical Co., Ltd., with a water content of less than 50ppm by weight), 30g of anhydrous magnesium chloride (commercially purchased from Fushun City Xinyi titanium factory), 50mL absolute ethanol (commercially purchased from Beijing Chemical Plant, the water content is less than 100ppm by weight), 1mL 2-methoxybenzoyl chloride (commercially purchased from TOKYOKASEI KOGYO CO.LTD) and 0.15g water, heated to 120°C with stirring. After 2 hours of constant temperature reaction, the mixture was pressed into 300 mL of methyl silicone oil (commercially purchased from Dow Corning, with a viscosity of 300 centipoise / 20° C., and a water content of less than 50 ppm by weight) preheated to 120 ° C. Stir for 30 minutes at a speed of 1 / min for emulsification. Then, the emulsified product was injected into 2L of hexane (by weight, water content less than 5ppm) pre-cooled to -30° ...

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Abstract

The present invention discloses a magnesium halide adduct MgX<1>Y-mR<1>OH-n(LB1)-k(LB2)-p(LB3), wherein LB1 is an alkoxyl benzoate compound represented by a formula II, LB2 is a hydroxybenzoate compound represented by a formula III, LB3 is R6OH, and in the differential scanning calorimetry graph of the magnesium halide adduct, within a temperature range of 5-220 DEG C, at least two melting peaks exist only within a temperature range of 90-120 DEG C, and the melting enthalpy value corresponding to the highest melting temperature is 160 J / g or more. According to the present invention, the catalyst system formed through a reaction of the magnesium halide adduct, a titanium compound and an optionally electron donor shows high polymerization activity when the catalyst system is adopted as the catalyst of olefin polymerization, especially propylene polymerization, and maintains high stereospecific ability, and the obtained polymer has good morphology. The formulas II and III are defined in the specification.

Description

technical field [0001] The present invention relates to a magnesium halide adduct and its application. The present invention also relates to a catalyst component for olefin polymerization and its application. The present invention further relates to a catalyst system for olefin polymerization and its application. The invention further relates to a process for the polymerization of olefins. Background technique [0002] It is known in the prior art to support titanium compounds and electron donor compounds on active magnesium halides to prepare Ziegler-Natta catalysts. Among them, the active magnesium halide often uses the adduct of magnesium halide and alcohol, which is used as a carrier to react with titanium halide and electron donor compound to obtain a spherical catalyst. The spherical catalyst is used in olefins (especially propylene) During polymerization, it has higher polymerization activity and stereospecific ability, and the obtained polymer also has better partic...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F3/02C08F10/06C08F10/00C08F4/646C08F4/649
Inventor 张纪贵夏先知刘月祥李威莅高富堂高平凌永泰赵瑾彭人琪谭扬林洁张志会段瑞林
Owner CHINA PETROLEUM & CHEM CORP
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