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Catalyst component used for vinyl polymerization, preparation method and application

An ethylene polymerization and catalyst technology, applied in the field of olefin polymerization, can solve the problems of unsatisfactory hydrogen adjustment sensitivity, complicated operation and high production cost

Active Publication Date: 2012-05-02
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In the above-mentioned published patents, in order to make the catalyst applicable to the gas-phase fluidized bed polymerization process, there are stricter requirements on the average particle size, surface area, and pore size of the carrier silica used, and the price of this carrier is relatively high. At the same time, the silica carrier needs to be activated before use, which will increase the production cost of the catalyst; and the active component of the catalyst is loaded on the carrier by impregnation and other methods. Due to the limitation of the amount of titanium loaded, the catalyst Efficiency is not satisfactory
In addition, the amount of fine powder in the polyethylene powder produced by using this catalyst is relatively large, and the particles below 150 microns usually account for about 15wt% of the whole powder, which is undesirable in industrial production.
[0005] The catalyst production method mentioned in the Chinese patent CN 1085915A, although overcomes some shortcomings mentioned above, needs to use metal magnesium as a reducing agent in the production process, and still needs to use a large amount of silica carrier substances, and finally needs The method of spray drying is still required to obtain catalyst particle products, which requires large equipment investment and complicated operation, so that the overall production cost is still high
[0006] In the Chinese patent CN85100997, a catalyst for olefin polymerization is disclosed, which is formed by dissolving magnesium halide in organic epoxy compounds and organic phosphorus compounds to form a uniform solution, and then giving it with at least one precipitation aid and a polycarboxylic acid ester. It is prepared by the action of electron bodies and transition metal titanium halides and their derivatives. When the catalyst is used for propylene polymerization, it shows high polymerization activity and good stereospecificity, but when it is used for ethylene polymerization, the activity is low. , and the particle size distribution of the polymer is wide, and the sensitivity to hydrogen adjustment is not ideal
However, due to the preparation of the solid catalyst component using the pre-prepared alkoxymagnesium carrier, the production cost of the catalyst obtained in the process of industrial realization of this production method is relatively high, and the sphericity of the obtained catalyst is relatively poor

Method used

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  • Catalyst component used for vinyl polymerization, preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] 1. Preparation of catalyst components

[0056] In a four-neck flask equipped with a stirrer, install a reflux condenser and connect a cumulative gas meter to the reflux condenser. After the entire reaction device is fully replaced by nitrogen, add 70.8ml of absolute ethanol and 1.26g of iodine to the container. , to dissolve it. Add 6g metal magnesium inside, be warming up to the reflux temperature of ethanol under stirring condition, add absolute ethanol 47ml every 10 minutes from reflux, magnesium powder 6g, altogether 3 times. About 1 to 2 hours after the completion of the third addition, the liquid viscosity began to rise sharply (at this time, the reaction rate can be calculated to be about 85% through the amount of hydrogen generated), at this time, add 259ml of ethanol to the reaction system, and continue the reaction until The whole reaction time is about 6 hours until no hydrogen gas is produced at the end of the reaction. The solid was washed three times wit...

Embodiment 2

[0064] Catalyst preparation method is the same as embodiment 1.

[0065] Polymerization evaluation conditions: a stainless steel reaction kettle with a volume of 2 liters, fully replaced by hydrogen gas, injecting about 0.5 liters of hexane with nitrogen, injecting 2 ml of triethylaluminum-hexane solution with a concentration of 1 mmol / ml with a syringe, and stirring Then add 10 mg of titanium-containing solid catalyst component, and make up about 1 liter of hexane in total.

[0066] After the feeding is completed, the temperature is raised and hydrogen and ethylene are introduced successively, of which 6.8×10 5 H 2 , 3.5×10 5 Pa ethylene, the polymerization temperature is 85°C, react for two hours, lower the temperature, drain the residual pressure in the kettle, release the polymer slurry material, filter off the hexane, dry the polymer to obtain polyethylene powder, the results are shown in Table 1.

Embodiment 3

[0068] The catalyst preparation method is the same as in Example 1, and the 2,2,2-trichloroethanol hexane solution (0.1M) is changed to 2ml.

[0069] After evaporating and drying, 6.5 g of granular titanium-containing solid catalyst components were obtained, including 1.98% Ti and 19.1% (by weight) of tetrahydrofuran.

[0070] Polymerization evaluation conditions are the same as in Example 1, and the results are shown in Table 1.

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Abstract

The invention provides a titaniferous solid catalyst component used for vinyl polymerization and a preparation method. The titaniferous solid catalyst component is prepared according to the following three continuous steps: 1) under the existence of halogen or halogen-containing compound, reacting metal magnesium with alcohol, thereby preparing a magnesium-containing solid; 2) utilizing an organic metallic compound or a mixture of the organic metallic compound and an electron donor compound to process the magnesium-containing solid, thereby obtaining a magnesium-containing catalyst carrier; and 3) under the existence of an inert organic solvent, utilizing a compound of transition metal titanium to process the magnesium-containing catalyst carrier, and then utilizing a halogenated alcohol compound to process, thereby obtaining the catalyst component. The preparation method has the characteristics of simple process, convenience in operation, low investment in industrial equipment, easiness in controlling the product quality, and the like. The titaniferous solid catalyst component has the characteristics of high vinyl polymerization catalytic activity, high copolymerizing capacity, high stacking density of polymer, less subdivision, and the like. The titaniferous solid catalyst component is suitable for slurry polymerization or gas-phase polymerization of vinyl, and is especiallysuitable for a gas-phase fluidized bed polymerization process for the vinyl, in which the catalyst is fed in a slurry form.

Description

technical field [0001] The invention relates to a titanium-containing solid catalyst component for ethylene polymerization, a preparation method and application, and belongs to the field of olefin polymerization. technical background [0002] With the development of the world's polyolefin industry, the continuous improvement and innovation of polyolefin production technology has made the polyolefin industry have higher and higher requirements for catalysts, and many different types of polyolefin catalysts have also appeared. [0003] In the polymerization of olefins, especially the homopolymerization of ethylene or the copolymerization of ethylene and α-olefins, catalyst components based on magnesium, titanium, halogen and electron donors are mostly used. When this type of catalyst is used in a gas-phase fluidized bed polymerization process, in order to ensure that the catalyst particle shape and particle size distribution are more suitable for fluidized state operation, the...

Claims

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Application Information

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IPC IPC(8): C08F110/02C08F210/16C08F4/645C08F4/654C08F4/655C08F4/658C08F4/649C08F4/02
Inventor 寇鹏杨岭李秉毅黄庭马永华王丽莎
Owner CHINA PETROLEUM & CHEM CORP
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