Supported single metallocene catalyst for ethylene polymerization

Abstract

The invention discloses a supported single metallocene catalyst used for vinyl polymerization and a preparation method thereof. The catalyst comprises a single metallocene compound, a chlorinated alkyl silicon modifier, alkyl aluminoxane and a magnesium chloride carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated alkyl silicon modified magnesium chloride carrier, 2) preparation of an alkyl aluminoxane modified magnesium chloride carrier, and 3)preparation of a magnesium chloride supported single metallocene catalyst; and the obtained single metallocene catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the magnesium chloride carrier is simple, and the obtained supported catalyst particles have good morphology with adjustable size. The obtained supported single metallocene catalyst is capable of catalyzing copolymerization of ethylene and alpha-alkene, the copolymerization activity is high, the obtained resin powder has good particle morphology, bulk density is high, and the single metallocene catalyst is suitable for the polymerization technology of a slurry method and a gas phase method.

Description

technical field

[0001] The invention relates to a modified magnesium chloride supported monometallocene catalyst, a preparation method, and an application of the obtained catalyst in olefin polymerization. technical background

[0002] The development and application of single metallocene catalysts is another major breakthrough in the field of olefin polymerization catalysts after the traditional Ziegler-Natta catalysts. Especially in the 1980s, Kaminsky and Sinn et al. (Angew.Chem., 1980, 19, 390; Adv Organoment.Chem., 1980, 18, 99) developed a high-efficiency cocatalyst methylaluminoxane (MAO), making the research on single metallocene catalysts enter a stage of rapid development. Because the homogeneous single metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process to overcome the above problems...

Examples

Embodiment 1

[0051] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0052] Under the protection of nitrogen, take 5.62 grams of magnesium chloride carrier and add 100 ml of dried hexane to disperse into a suspension, add 1 ml of SiCl 2 (n-Bu) 2 , start stirring, heat up to 30° C., react for 4 hours, and dry in vacuum to obtain a solid powder with good fluidity.

[0053] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0054] Under nitrogen protection, take 5.0 grams of the modified magnesium chloride carrier obtained above and add it to a glass reactor, add 60 milliliters of dried toluene, disperse into a suspension, and add 18 milliliters of 10 wt% MAO (methylaluminoxane) toluene solution , heated to 50 ° C, stirred for 4 hours, then washed three times with 50 ml × 3 toluene, then washed with hexane, and dried in vacuum to obtain a solid powder with good fluidity, that is, a magnesium chloride carrier conta...

Embodiment 2

[0063] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0064] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0065] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0066] Same as step (2) of Example 1.

[0067] (3) Preparation of supported metallocene catalyst B

[0068] Same as step (3) of Example 1 to obtain supported metallocene catalyst B. Characterized by ICP, in catalyst B, the weight content of Ti is 0.31%, and the weight content of Al is 11.30%.

Embodiment 3

[0070] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0071] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to CH 3 SiCl 3 .

[0072] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0073] Same as step (2) of Example 1.

[0074] (3) Preparation of supported metallocene catalyst C

[0075] Same as step (3) of Example 1 to obtain supported metallocene catalyst C. Characterized by ICP, the weight content of Ti in catalyst C is 0.30%, and the weight content of Al is 11.18%.

technical field

[0001] The invention relates to a modified magnesium chloride supported monometallocene catalyst, a preparation method, and an application of the obtained catalyst in olefin polymerization. technical background

[0002] The development and application of single metallocene catalysts is another major breakthrough in the field of olefin polymerization catalysts after the traditional Ziegler-Natta catalysts. Especially in the 1980s, Kaminsky and Sinn et al. (Angew.Chem., 1980, 19, 390; Adv Organoment.Chem., 1980, 18, 99) developed a high-efficiency cocatalyst methylaluminoxane (MAO), making the research on single metallocene catalysts enter a stage of rapid development. Because the homogeneous single metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process to overcome the above problems...

Examples

Embodiment 1

[0051] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0052] Under the protection of nitrogen, take 5.62 grams of magnesium chloride carrier and add 100 ml of dried hexane to disperse into a suspension, add 1 ml of SiCl 2 (n-Bu) 2 , start stirring, heat up to 30° C., react for 4 hours, and dry in vacuum to obtain a solid powder with good fluidity.

[0053] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0054] Under nitrogen protection, take 5.0 grams of the modified magnesium chloride carrier obtained above and add it to a glass reactor, add 60 milliliters of dried toluene, disperse into a suspension, and add 18 milliliters of 10 wt% MAO (methylaluminoxane) toluene solution , heated to 50 ° C, stirred for 4 hours, then washed three times with 50 ml × 3 toluene, then washed with hexane, and dried in vacuum to obtain a solid powder with good fluidity, that is, a magnesium chloride carrier conta...

Embodiment 2

[0063] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0064] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0065] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0066] Same as step (2) of Example 1.

[0067] (3) Preparation of supported metallocene catalyst B

[0068] Same as step (3) of Example 1 to obtain supported metallocene catalyst B. Characterized by ICP, in catalyst B, the weight content of Ti is 0.31%, and the weight content of Al is 11.30%.

Embodiment 3

[0070] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0071] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to CH 3 SiCl 3 .

[0072] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0073] Same as step (2) of Example 1.

[0074] (3) Preparation of supported metallocene catalyst C

[0075] Same as step (3) of Example 1 to obtain supported metallocene catalyst C. Characterized by ICP, the weight content of Ti in catalyst C is 0.30%, and the weight content of Al is 11.18%.

Images