Magnesium alkoxide catalyst support and the preparation method and use thereof

Abstract

A magnesium alkoxide catalyst support and the preparation method and use thereof are provided. The method for preparing the magnesium alkoxide catalyst support comprises the following steps: mixing a metallic magnesium, a monohydric alcohol, a halogenating agent and a surfactant at 0° C. to 90° C. under an inert gas atmosphere, and then washing the resultant with an inert solvent to obtain the magnesium alkoxide catalyst support. A magnesium alkoxide catalyst support obtained by the above method is also provided, which can be used to catalyze olefin polymerization. The magnesium alkoxide catalyst support obtained by the above method according to the invention has excellent particle morphology and controllable size, and is suitable for preparing a catalyst for olefin polymerization.

Claims

1. A method for preparing a magnesium alkoxide catalyst support, comprising the following steps: mixing a metallic magnesium, a monohydric alcohol, a halogenating agent and a surfactant at 0° C. to 90° C. under an inert gas atmosphere, and then washing the resultant with an inert solvent to obtain the magnesium alkoxide catalyst support; wherein the monohydric alcohol is added in an amount of 2 mol to 50 mol, the halogenating agent is added in an amount of 0.0025 mol to 0.03 mol, and the inert organic solvent is added in an amount of 2 mol to 50 mol, based on 1 mol of the metallic magnesium; wherein the surfactant is added in a volume of from 0.01% to 10% based on the volume of the monohydric alcohol, and the surfactant is one or more selected from n-butyl titanate, tributyl phosphate, triphenyl phosphate, triethyl phosphite, 1,2-butanediol ditosylate, catechol di-p-tosylate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethylene glycol diacetate and triacetin.

2. The method for preparing a magnesium alkoxide catalyst support according to claim 1, wherein the metallic magnesium, the monohydric alcohol and the halogenating agent are added at one time or in batches.

3. The method for preparing a magnesium alkoxide catalyst support according to claim 2, wherein the metallic magnesium, the monohydric alcohol and the halogenating agent are added in batches.

4. The method for preparing a magnesium alkoxide catalyst support according to claim 1, wherein the metallic magnesium has a particle size of 0.5 μm to 300 μm.

5. The method for preparing a magnesium alkoxide catalyst support according to claim 1, wherein the monohydric alcohol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, n-nonanol, isononanol, n-decanol, isodecanol, phenol, phenyl methanol, phenyl ethanol, phenyl propanol, and any combinations thereof.

6. The method for preparing a magnesium alkoxide catalyst support according to claim 5, wherein the monohydric alcohol includes one or more selected from methanol, ethanol, propanol and butanol.

7. The method for preparing a magnesium alkoxide catalyst support according to claim 1, wherein the halogenating agent includes one or more selected from iodine, bromine, chlorine, magnesium iodide, magnesium bromide, magnesium chloride, calcium iodide, calcium bromide, calcium chloride, mercuric iodide, mercuric bromide, mercuric chloride, carbon tetraiodide, carbon tetrabromide, carbon tetrachloride and alkoxy magnesium halide.

8. The method for preparing a magnesium alkoxide catalyst support according to claim 7, wherein the halogenating agent includes one or more selected from iodine, carbon tetrachloride, magnesium iodide, magnesium chloride and alkoxy magnesium halide.

9. The method for preparing a magnesium alkoxide catalyst support according to claim 1, wherein the inert organic solvent includes one or more selected from hexane, heptane, octane, decane, benzene, toluene, xylene, chlorobenzene, a toluene derivative, a xylene derivative and a chlorobenzene derivative.

10. The method for preparing a magnesium alkoxide catalyst support according to claim 1, wherein the monohydric alcohol is added in an amount of 5 mol to 20 mol, and the halogenating agent is added in an amount of 0.0025 mol to 0.01 mol, based on 1 mol of the metallic magnesium.

Description

DETAILED DESCRIPTION

(1) The technical solutions of the present invention are described in detail as below for more distinct comprehension for the technical features, objects, and advantages of the present invention, which are not intended to limit the scope of the invention.

(2) Particle Size Distribution:

(3) The particle size of the magnesium alkoxide was determined using a Malvern MastersizerTMX;

(4) Average particle size (D50): a particle size corresponding to 50% cumulative weight;

(5) The particle size of the magnesium alkoxide and its distribution index Span=(D90−D10)/D50 are used to characterize the uniformity of the particle size distribution.

Example 1

(6) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(7) A reflux condenser, a thermometer and a burette were installed onto a reactor equipped with a stirrer. The top of the reflux condenser was connected with a conduit which was connected, on the other end, to an oil-sealing device to facilitate the observation of H.sub.2. After sufficient substitution with nitrogen, 2 g of magnesium powder, 10 mL of decane, 30 mL of absolute ethanol, 0.2 g of iodine and 1.5 mL of n-butyl titanate were added to the reactor. The resultant was warmed after the reaction is activated for 15 minutes, until the reaction temperature for the reaction system was reached. The step of adding magnesium powder, alcohol, iodine and decane in the same amount as the previous feed after H.sub.2 was no longer discharged from reaction system was repeated, such that the addition was carried out for 5 times in total. After the final batch was added and H.sub.2 was no longer produced by the reaction, the reaction system was aged for 2 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(8) The particle size and distribution of the product were measured using a particle size distribution meter. The results are shown in Table 1.

Example 2

(9) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(10) The same procedures as those in Example 1 were carried out, except that 1.5 mL of tributyl phosphate was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(11) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 3

(12) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(13) The same procedures as those in Example 1 were carried out, except that 1.5 mL of di-n-butyl phthalate was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(14) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 4

(15) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(16) The same procedures as those in Example 1 were carried out, except that 1.5 mL of ethylene glycol diacetate was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(17) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 5

(18) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(19) The same procedures as those in Example 1 were carried out, except that 1.5 mL of triacetin was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(20) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 6

(21) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(22) The same procedures as those in Example 1 were carried out, except that 0.5 mL of triacetin was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(23) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 7

(24) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(25) The same procedures as those in Example 1 were carried out, except that 1.5 mL of catechol di-p-tosylate was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(26) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 8

(27) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(28) The same procedures as those in Example 1 were carried out, except that 1.5 mL of triethyl phosphite was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(29) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Example 9

(30) This Example provides a magnesium alkoxide catalyst support which is prepared by the following procedures.

(31) The same procedures as those in Example 1 were carried out, except that 0.5 mL of n-butyl titanate and 0.5 mL of di-n-butyl phthalate were added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(32) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

Comparative Example 1

(33) The same procedures as those in Example 1 were carried out, except that no surfactant was added to the reaction system, and the reaction was carried out at 78° C. for 4 hours. Upon the completion of the final reaction, the product was washed, separated and dried to obtain a white solid powder with good fluidity.

(34) The obtained product was characterized in the same manner as that in Example 1. The results are shown in Table 1.

(35) TABLE-US-00001 TABLE 1 Particle Average particle size size distribution Particle shape D50 (μm) index Example 1 spherical 22.2 1.3 Example 2 spherical 43.7 1.2 Example 3 spherical 54.7 1.1 Example 4 spherical 39.3 1.1 Example 5 spherical 23.5 1.2 Example 6 spherical 16.5 1.3 Example 7 spherical 51.4 0.9 Example 8 spherical 42.5 1.3 Example 9 spherical 35.8 1.2 Comparative spherical 51.3 1.3 Example 1

(36) As can be seen from Table 1, when no surfactant was added in Comparative Example 1, only a support of about 50 μm was obtained with a limited size controlling range. In contrast, according to the preparation method in Example 1 magnesium alkoxide catalyst supports having various sizes were obtained by adjusting types of the surfactant.

(37) The above Examples show that the method for preparing a magnesium alkoxide catalyst support of the present invention can produce magnesium alkoxide particles having excellent particle morphology and uniform particle size distribution. Supports having various sizes can be obtained by changing types of surfactants, which support can be selectively used for various olefin polymerization processes. The inventive method has advantages which are apparent as compared with other methods. The magnesium alkoxide catalyst support prepared in the present invention is excellent as a support for catalyzing olefin polymerization.