Supported non-metallocene catalyst and preparation method and application thereof

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method thereof. The supported non-metallocene catalyst has the characteristics that the preparation process is simple, the content of a non-metallocene complex is controllable, and the copolymerization effect is obvious. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerization / copolymerization. And compared with the prior art, the application has the characteristics that activity is high in olefin polymerization catalysis, and a polymer has high bulk density and controllable molecular weight distribution.

Description

technical field

[0001] The present invention relates to a non-metallocene catalyst. Specifically, the present invention relates to a supported non-metallocene catalyst, its preparation method and its application in olefin homopolymerization / copolymerization. Background technique

[0002] The non-metallocene catalysts that appeared in the middle and late 1990s, also known as post-metallocene catalysts, the central atoms of the main catalysts include almost all transition metal elements, which have reached or even surpassed metallocene catalysts in some performance aspects, becoming The fourth generation of olefin polymerization catalysts after Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin product produced by this type of catalyst has excellent performance and low production cost. The coordination atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene groups or their derivative groups, such as ind...

Examples

preparation example Construction

[0092] According to the present invention, it relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: reacting a chemical treatment agent selected from Group IVB metal compounds with a porous support optionally subjected to thermal activation treatment to obtain a modified support; Dissolving the magnesium compound in a solvent to obtain a magnesium compound solution; contacting the modified carrier and the magnesium compound solution with a non-metallocene complex to obtain a mixed slurry; and adding a precipitant to the mixed slurry , the step of obtaining the supported non-metallocene catalyst.

[0093] The porous carrier will be specifically described below.

[0094] According to the present invention, as the porous support, for example, those organic or inorganic porous solids conventionally used as supports in the production of supported olefin polymerization catalysts in the art can be cited.

[0095] Specifically, examp...

Embodiment 1

[0287] The porous carrier is silicon dioxide, that is, silica gel, model ES757 of Ineos Company. First, the silica gel is thermally activated by continuously calcining at 600° C. for 4 hours under a nitrogen atmosphere.

[0288] The chemical treatment agent is titanium tetrachloride (TiCl 4 ). Weigh 5g of thermally activated silica gel, add 60ml of hexane, add titanium tetrachloride under normal temperature stirring conditions, react at 60°C for 2h, filter, wash with hexane 3 times, 60ml each time, and finally vacuum dry to obtain modified carrier.

[0289] Anhydrous magnesium chloride is used for the magnesium compound, and tetrahydrofuran is used as a solvent for dissolving the magnesium compound and the non-metallocene complex. The non-metallocene complex adopts the structure compound of.

[0290] Weigh anhydrous magnesium chloride and non-metallocene complexes, add tetrahydrofuran solvent and dissolve completely at room temperature to obtain a magnesium compound solut...

Embodiment 2

[0294] Basically the same as Example 1, but with the following changes:

[0295] The porous carrier was changed to Grace's 955, and it was continuously calcined at 400° C. for 8 hours under a nitrogen atmosphere to be thermally activated. The chemical treatment agent was changed to zirconium tetrachloride (ZrCl 4 ), hexane was changed to toluene.

[0296] Non-metallocene complexes using The solvent for dissolving the magnesium compound and the non-metallocene complex was changed to toluene, the precipitating agent was changed to cyclohexane, and finally vacuum-dried at 60° C. to obtain a supported non-metallocene catalyst.

[0297] Wherein the ratio is that the mass ratio of the magnesium compound to the porous carrier is 1:1; in terms of Mg element, the molar ratio of the magnesium compound to the non-metallocene complex is 1:0.14, and the ratio of the magnesium compound to the non-metallocene complex is 1mol:160ml, and the chemical treatment The molar ratio of the agent ...

technical field

[0001] The present invention relates to a non-metallocene catalyst. Specifically, the present invention relates to a supported non-metallocene catalyst, its preparation method and its application in olefin homopolymerization / copolymerization. Background technique

[0002] The non-metallocene catalysts that appeared in the middle and late 1990s, also known as post-metallocene catalysts, the central atoms of the main catalysts include almost all transition metal elements, which have reached or even surpassed metallocene catalysts in some performance aspects, becoming The fourth generation of olefin polymerization catalysts after Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin product produced by this type of catalyst has excellent performance and low production cost. The coordination atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene groups or their derivative groups, such as ind...

Examples

preparation example Construction

[0092] According to the present invention, it relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: reacting a chemical treatment agent selected from Group IVB metal compounds with a porous support optionally subjected to thermal activation treatment to obtain a modified support; Dissolving the magnesium compound in a solvent to obtain a magnesium compound solution; contacting the modified carrier and the magnesium compound solution with a non-metallocene complex to obtain a mixed slurry; and adding a precipitant to the mixed slurry , the step of obtaining the supported non-metallocene catalyst.

[0093] The porous carrier will be specifically described below.

[0094] According to the present invention, as the porous support, for example, those organic or inorganic porous solids conventionally used as supports in the production of supported olefin polymerization catalysts in the art can be cited.

[0095] Specifically, examp...

Embodiment 1

[0287] The porous carrier is silicon dioxide, that is, silica gel, model ES757 of Ineos Company. First, the silica gel is thermally activated by continuously calcining at 600° C. for 4 hours under a nitrogen atmosphere.

[0288] The chemical treatment agent is titanium tetrachloride (TiCl 4 ). Weigh 5g of thermally activated silica gel, add 60ml of hexane, add titanium tetrachloride under normal temperature stirring conditions, react at 60°C for 2h, filter, wash with hexane 3 times, 60ml each time, and finally vacuum dry to obtain modified carrier.

[0289] Anhydrous magnesium chloride is used for the magnesium compound, and tetrahydrofuran is used as a solvent for dissolving the magnesium compound and the non-metallocene complex. The non-metallocene complex adopts the structure compound of.

[0290] Weigh anhydrous magnesium chloride and non-metallocene complexes, add tetrahydrofuran solvent and dissolve completely at room temperature to obtain a magnesium compound solut...

Embodiment 2

[0294] Basically the same as Example 1, but with the following changes:

[0295] The porous carrier was changed to Grace's 955, and it was continuously calcined at 400° C. for 8 hours under a nitrogen atmosphere to be thermally activated. The chemical treatment agent was changed to zirconium tetrachloride (ZrCl 4 ), hexane was changed to toluene.

[0296] Non-metallocene complexes using The solvent for dissolving the magnesium compound and the non-metallocene complex was changed to toluene, the precipitating agent was changed to cyclohexane, and finally vacuum-dried at 60° C. to obtain a supported non-metallocene catalyst.

[0297] Wherein the ratio is that the mass ratio of the magnesium compound to the porous carrier is 1:1; in terms of Mg element, the molar ratio of the magnesium compound to the non-metallocene complex is 1:0.14, and the ratio of the magnesium compound to the non-metallocene complex is 1mol:160ml, and the chemical treatment The molar ratio of the agent ...

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