CN108102014B - Components and preparation method of spherical alkoxy magnesium particles - Google Patents
Components and preparation method of spherical alkoxy magnesium particles Download PDFInfo
- Publication number
- CN108102014B CN108102014B CN201810018038.XA CN201810018038A CN108102014B CN 108102014 B CN108102014 B CN 108102014B CN 201810018038 A CN201810018038 A CN 201810018038A CN 108102014 B CN108102014 B CN 108102014B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- alcohol
- particles
- spherical
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
Abstract
The invention discloses a component of spherical alkoxy magnesium particles and a method for preparing the spherical alkoxy magnesium particles. The invention introduces a certain amount of anhydrous magnesium phenylcarboxylate into alcohol or mixed alcohol compounds, and the anhydrous magnesium phenylcarboxylate is in contact reaction with magnesium powder to prepare alkoxy magnesium; the obtained alkoxy magnesium particles have perfect shapes, high sphericity, higher stacking density and uniform and narrow particle size distribution. Meanwhile, the alkoxy magnesium particles can be used for preparing olefin polymerization catalysts.
Description
Technical Field
The invention relates to the field of preparation of alkoxy magnesium, in particular to a component of spherical alkoxy magnesium particles and a method for preparing the spherical alkoxy magnesium particles by using the component.
Background
As is well known, with the development of economy, the demand of polyolefin materials is higher and higher nowadays, and the high-efficiency polyolefin catalyst for producing polyolefin materials is widely applied in the field of polyolefin catalysts due to the well-controlled particle morphology and microstructure. The key role is the composition and microstructure of the carrier, and the carriers obtained by different methods correspondingly obtain catalysts with different structures and performances.
The use of magnesium alkoxides as supports for high performance catalysts is disclosed in a number of patent documents, and catalysts prepared with magnesium alkoxides supports have significantly higher activity, good hydrogen response and excellent copolymerisation performance. In recent years, there are various methods for preparing magnesium alkoxide reported in published technical literature, and the following methods are mainly used: one is a method in which magnesium metal is reacted with an alcohol in the presence of iodine to obtain spherical or ellipsoidal magnesium diethoxide as disclosed in Japanese patent laid-open Nos. 03-74341 and 04-368391, however, it is difficult to control the reaction rate appropriately, the obtained product is inevitably produced in the form of non-uniform large particles or fine powder, and the bulk density is generally low; another method is a spray drying process of diethoxymagnesium alcohol solution disclosed in Japanese patent laid-open No. 6-8733, which can prepare spherical particles and then perform decarboxylation treatment, and the process is complicated and expensive, and the obtained product is difficult to decarboxylate completely, and the product quality is difficult to meet the downstream use; in addition, there is a method in which magnesium metal is reacted with alcohol to obtain magnesium alkoxide, and then the magnesium alkoxide is mechanically ground to control the particle size, and this method has a problem in that the obtained product has non-uniform particle size, which seriously affects the use.
The invention aims to overcome the defects in the prior art and obtain regular spherical alkoxy magnesium particles with good morphology by adopting a simpler and more practical preparation method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a component of spherical alkoxy magnesium particles, the spherical alkoxy magnesium particles prepared by the component have perfect shapes, high sphericity and higher bulk density, and the bulk density is more than or equal to 0.30 g/mL; the particles are uniform and have narrow particle size distribution, and the particle size distribution is less than or equal to 1.2; can be used as a carrier for preparing olefin polymerization catalysts. Another object of the present invention is to provide a method for preparing spherical magnesium alkoxide particles.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composition of spherical magnesium alkoxide particles, the composition comprising the following components: metal magnesium powder, alcohol or mixed alcohol compound, iodine simple substance and anhydrous magnesium phenylcarboxylate.
Further, the molar ratio of the alcohol or mixed alcohol compound to the metal magnesium powder is as follows: 2-40; the molar ratio of the iodine simple substance to the metal magnesium powder is as follows: 0.0001 to 0.2; the proportion of the anhydrous magnesium phenylcarboxylate added into the alcohol or the mixed alcohol compound is 0.01-200 g/L.
Further, the alcohol or mixed alcohol compound is shown as a general formula R1OH, wherein R is1Is C1～C20The hydrocarbon group of (b) may be a saturated or unsaturated linear, branched or cyclic chain.
Further, the alcohol or mixed alcohol compound includes, but is not limited to, a mixture of one or more of methanol, ethanol, isopropanol, n-butanol, n-hexanol, isooctanol, benzyl alcohol, and phenethyl alcohol.
Further, the molar ratio of the alcohol or mixed alcohol compound to the metal magnesium powder is as follows: 4 to 30.
Further, the molar ratio of the iodine simple substance to the metal magnesium powder is as follows: 0.001 to 0.1.
Further, the proportion of the anhydrous magnesium phenylcarboxylate to the alcohol or mixed alcohol compound is 0.1-100 g/L.
Further, the anhydrous magnesium phenylcarboxylate is shown as the general formula (R)2COO)2Mg, wherein R is2As shown in the general formula CnH2n-7Wherein n is more than or equal to 6 and less than or equal to 16.
Further, the aromatic alkyl magnesium carboxylate includes but is not limited to a mixture of one or more of magnesium benzoate and magnesium phenylacetate.
A method of making spherical magnesium alkoxide particles, the method comprising: under the protection of inert gas, dissolving the anhydrous magnesium phenylcarboxylate in the alcohol or mixed alcohol compound, dissolving the iodine simple substance in the alcohol or mixed alcohol compound, adding the metal magnesium powder, and heating to the reflux temperature to maintain the reaction until no gas is generated; and washing and drying the solid product generated by the reaction to obtain the alkoxy magnesium particles.
Further, the spherical magnesium alkoxide particles prepared by the method have an average particle diameter of 15 to 120 microns and a particle size distribution Span ═ d90 to d10)/d50 of less than or equal to 1.2.
Further, the spherical magnesium alkoxide particles produced by the method have a bulk density greater than or equal to 0.30 g/mL.
The invention has the following beneficial technical effects:
1. the reaction material composition is simple, and the production cost is favorably reduced;
2. after the anhydrous magnesium phenylcarboxylate is introduced, the obtained large particles and fine powder of the alkoxy magnesium particles are less, and the particle size distribution is narrower;
3. the alkoxy magnesium particles have perfect shapes, are close to perfect spheres, and have proper composition and structure for being used as a carrier of an olefin polymerization catalyst.
Detailed Description
Hereinafter, embodiments of the present invention will be described in further detail with reference to examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The invention provides a component of spherical alkoxy magnesium particles, which comprises the following components: metal magnesium powder, alcohol or mixed alcohol compound, iodine simple substance and anhydrous magnesium phenylcarboxylate; wherein, the mol ratio of the alcohol or the mixed alcohol compound to the metal magnesium powder is as follows: 2 to 40, preferably 4 to 30, when the amount of the alcohol or the mixed alcohol compound is too small, the viscosity of the reaction system is rapidly increased, and the reaction system cannot be effectively and uniformly dispersed, so that the generated particles are deteriorated, and when the amount of the alcohol or the mixed alcohol compound is too large, the stacking density of the generated magnesium alkoxide particles is generally low, the strength of the particles is also poor, and the performance improvement of a subsequent catalyst is not facilitated. The molar ratio of the iodine simple substance to the metal magnesium powder is as follows: 0.0001 to 0.2, preferably 0.001 to 0.1, to control a suitable initial reaction rate. The proportion of the anhydrous magnesium phenylcarboxylate to the alcohol or the mixed alcohol compound is 0.01-200 g/L, and the preferable proportion is 0.1-100 g/L.
In the method for preparing the magnesium alkoxide particles, the shape of the used magnesium metal powder particles is not strictly limited, but the powder with the average particle size of 5-350 microns, preferably 20-200 microns is required, so that the average particle size of the generated magnesium alkoxide particles is controlled to be 15-120 microns, the reactivity of the particles can be ensured to be relatively uniform, and the particle shape of the magnesium alkoxide particles is relatively perfect and uniform.
The alcohol or mixed alcohol compound in the invention includes but is not limited to one or more of methanol, ethanol, isopropanol, n-butanol, n-hexanol, isooctanol, benzyl alcohol and phenethyl alcohol; ethanol is preferred. In order to ensure the excellent performance of the prepared alkoxy magnesium, the water content in the alcohol is preferably as low as possible, generally controlled to be less than 1000ppm, preferably less than 200 ppm.
The adding sequence of the reaction raw materials in the method for preparing the spherical alkoxy magnesium particles is not strictly specified, and can be determined according to requirements. The magnesium powder can be added at one time or added in batches, the reaction rate can be controlled well by adding in batches, the reaction can be carried out at 0-100 ℃, generally, the reaction rate is faster when the temperature is higher, and the reaction is better controlled at the reflux temperature. The reaction time is generally 1 to 20 hours, preferably 2 to 10 hours, until no gas is generated. The solid product after the reaction may be washed several times with a mixed alcohol before the reaction or ordinary ethanol (water content less than 200ppm), or may be washed with an inert organic solvent such as hexane, toluene, etc., and then dried to obtain magnesium alkoxide particles. The whole process is completed under the protection of inert gas, wherein the inert gas is helium, argon or nitrogen.
The invention will be further illustrated with reference to specific examples:
example 1
Fully replacing a reactor with high-purity nitrogen, sequentially adding 0.20 g of anhydrous magnesium phenylcarboxylate, 25 ml of absolute ethyl alcohol and 0.15 g of iodine under the protection of nitrogen, stirring for dissolving, heating, adding 1.0 g of 80-150-mesh magnesium powder and 10 ml of absolute ethyl alcohol, maintaining reflux reaction, adding 1.0 g of 80-150-mesh magnesium powder and 10 ml of absolute ethyl alcohol again at intervals of 20 minutes, adding 4.0 g of magnesium powder and 65 ml of absolute ethyl alcohol in 4 times, maintaining reflux reaction for 3 hours after the materials are added, washing twice with absolute ethyl alcohol, wherein the amount of absolute ethyl alcohol is 80 ml each time, washing twice with hexane, the amount of hexane is 100 ml each time, and drying to obtain off-white solid flowable powder after the washing is finished, wherein the specific result is shown in table 1.
Example 2
This example differs from example 1 only in that: the '25 ml of absolute ethanol' which is initially added is adjusted to '40 ml of absolute ethanol', and the '80-150 mesh magnesium powder' is adjusted to '100-200 mesh magnesium powder'.
Example 3
This example differs from example 1 only in that: the "0.20 g of anhydrous magnesium phenylcarboxylate" in example 1 was adjusted to "0.50 g of anhydrous magnesium phenylcarboxylate".
Example 4
This example differs from example 1 only in that: the "0.15 g iodine" in example 1 was adjusted to "0.40 g iodine".
Example 5
This example differs from example 1 only in that: the "0.20 g of anhydrous magnesium phenylcarboxylate" in example 1 was adjusted to "1.0 g of anhydrous magnesium phenylcarboxylate", and 5 ml of isooctyl alcohol was added.
Comparative example 1
Fully replacing a reactor with high-purity nitrogen, sequentially adding 25 ml of absolute ethyl alcohol and 0.15 g of iodine under the protection of nitrogen, stirring to dissolve, heating, adding 1.0 g of 80-150-mesh magnesium powder and 10 ml of absolute ethyl alcohol, maintaining a reflux reaction, adding 1.0 g of 80-150-mesh magnesium powder and 10 ml of absolute ethyl alcohol again at intervals of 20 minutes, adding 4.0 g of magnesium powder and 65 ml of absolute ethyl alcohol in 4 times, maintaining the reflux reaction for 3 hours after adding materials, washing twice with absolute ethyl alcohol, wherein the amount of absolute ethyl alcohol in each time is 80 ml, washing twice with hexane, the amount of hexane in each time is 100 ml, and drying to obtain off-white solid flowable powder after washing is finished, wherein specific results are shown in table 1.
Example 6
The magnesium alkoxide particles prepared by the invention can be used for synthesizing catalyst components for olefin polymerization: adding 50 ml of titanium tetrachloride into a reactor repeatedly replaced by high-purity nitrogen, cooling to 0 ℃, adding 5 g of alkoxy magnesium particles obtained in example 1, slowly heating to 80 ℃, adding 1.5 ml of DIBP (diisobutyl phthalate), continuously heating to 110, maintaining the reaction for 2 hours, then performing pressure filtration on the liquid to be clean, adding 50 ml of titanium tetrachloride again, heating to 110, maintaining the reaction for 2 hours, performing pressure filtration on the liquid to be clean, repeating the process again, washing the obtained solid for 3 times at 50 ℃ by using 100 ml of hexane, and finally drying to obtain solid catalyst powder.
Polymerization of propylene: after the reactor was purged with high-purity nitrogen gas by full displacement, 1.5mmol of triethylaluminum and 0.1mmol of diphenyldimethoxysilane were added, 10mg of the above catalyst was further added, 2.5L of liquid propylene and 1L of hydrogen (under a standard condition) were added under stirring, and the reaction was maintained at 70 ℃ for 1 hour to obtain 727 g of a polymer having a bulk density of 0.43g/ml and a melt index of 5.89g/10 min.
TABLE 1
As shown in Table 1, the magnesium alkoxide prepared in examples 1 to 5 had a good particle morphology, a high bulk density and a narrow particle distribution, compared to the comparative example. Meanwhile, from the results of example 6, the catalyst prepared by using the magnesium alkoxide particles has high propylene polymerization activity and high bulk density, and is suitable for the production of polypropylene.
The test method involved in the invention is as follows:
1. particle size and distribution of support and catalyst: the MASTERSIZE particle size distribution instrument uses n-hexane as a dispersing agent, and the measuring range is 0.02-2000 mu m. span ═ D90-D10)/D50.
2. Determination of bulk density: DIN-53194.
3. The aluminum content was measured using an ICP-AES inductively coupled plasma emission spectrometer.
The above description is only for the purpose of illustrating the present invention, and it should be understood that the present invention is not limited to the above embodiments, and various modifications conforming to the spirit of the present invention are within the scope of the present invention.
Claims (10)
1. Spherical alkoxy magnesium particles are characterized by being prepared from the following components: the magnesium powder comprises metal magnesium powder, alcohol or mixed alcohol compound, iodine simple substance and anhydrous magnesium phenylcarboxylate, wherein the molar ratio of the alcohol or mixed alcohol compound to the metal magnesium powder is as follows: 2-40; the molar ratio of the iodine simple substance to the metal magnesium powder is as follows: 0.0001 to 0.2; the proportion of the anhydrous magnesium phenylcarboxylate added into the alcohol or the mixed alcohol compound is 01-100 g/L; under the protection of inert gas, dissolving the anhydrous magnesium phenylcarboxylate in the alcohol or mixed alcohol compound, dissolving the iodine simple substance in the alcohol or mixed alcohol compound, adding the metal magnesium powder, and heating to the reflux temperature to maintain the reaction until no gas is generated; and washing and drying the solid product generated by the reaction to obtain the alkoxy magnesium particles.
2. The spherical magnesium alkoxide particles of claim 1, wherein the alcohol or mixed alcohol compound is of formula R1OH, wherein R is1Is C1～C20The hydrocarbon group of (b) is a saturated or unsaturated linear, branched or cyclic chain.
3. The spherical magnesium alkoxide particles according to claim 1, wherein the alcohol or mixed alcohol compound comprises a mixture of one or more of methanol, ethanol, isopropanol, n-butanol, n-hexanol, isooctanol, benzyl alcohol, phenethyl alcohol.
4. The spherical magnesium alkoxide particles according to claim 1, wherein the molar ratio of the alcohol or mixed alcohol compound to the magnesium metal powder is: 4 to 30.
5. The spherical magnesium alkoxide particle as set forth in claim 1, wherein the molar ratio of elemental iodine to magnesium metal powder is: 0.001 to 0.1.
6. The spherical magnesium alkoxide particles of claim 1, wherein the anhydrous magnesium phenylcarboxylate is of formula (R)2COO)2Mg, wherein R is2As shown in the general formula CnH2n-7Wherein n is more than or equal to 6 and less than or equal to 16.
7. The spherical magnesium alkoxide particles of claim 6, wherein the magnesium aryl carboxylate comprises a mixture of one or more of magnesium benzoate and magnesium phenylacetate.
8. The preparation method of the spherical alkoxy magnesium particles is characterized in that the spherical alkoxy magnesium particles are prepared from the following components: the magnesium powder comprises metal magnesium powder, alcohol or mixed alcohol compound, iodine simple substance and anhydrous magnesium phenylcarboxylate, wherein the molar ratio of the alcohol or mixed alcohol compound to the metal magnesium powder is as follows: 2-40; the molar ratio of the iodine simple substance to the metal magnesium powder is as follows: 0.0001 to 0.2; the proportion of the anhydrous magnesium phenylcarboxylate added into the alcohol or the mixed alcohol compound is 0.1-100 g/L; under the protection of inert gas, dissolving the anhydrous magnesium phenylcarboxylate in the alcohol or mixed alcohol compound, dissolving the iodine simple substance in the alcohol or mixed alcohol compound, adding the metal magnesium powder, and heating to the reflux temperature to maintain the reaction until no gas is generated; and washing and drying the solid product generated by the reaction to obtain the alkoxy magnesium particles.
9. The method according to claim 8, wherein the spherical magnesium alkoxide particles produced by the method have an average particle diameter of 15 to 120 μm and a particle diameter distribution Span = (d90-d10)/d50 of 1.2 or less.
10. The method of claim 8, wherein the spherical magnesium alkoxide particles produced by the method have a bulk density of 0.30g/mL or greater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810018038.XA CN108102014B (en) | 2018-01-09 | 2018-01-09 | Components and preparation method of spherical alkoxy magnesium particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810018038.XA CN108102014B (en) | 2018-01-09 | 2018-01-09 | Components and preparation method of spherical alkoxy magnesium particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108102014A CN108102014A (en) | 2018-06-01 |
| CN108102014B true CN108102014B (en) | 2020-10-27 |
Family
ID=62219592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810018038.XA Active CN108102014B (en) | 2018-01-09 | 2018-01-09 | Components and preparation method of spherical alkoxy magnesium particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108102014B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477639A (en) * | 1983-05-27 | 1984-10-16 | Shell Oil Company | Olefin polymerization catalyst component and composition and method of preparation |
| JPS60110704A (en) * | 1983-11-22 | 1985-06-17 | Idemitsu Kosan Co Ltd | Production of polyolefin |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU61917A1 (en) * | 1970-10-23 | 1972-06-28 | ||
| US4158642A (en) * | 1977-04-25 | 1979-06-19 | Exxon Research & Engineering Co. | Trialkyl aluminum cocatalyst |
| JPS5670005A (en) * | 1979-11-09 | 1981-06-11 | Mitsubishi Petrochem Co Ltd | Component of catalyst for olefin polymerization |
| JPS58222103A (en) * | 1982-06-18 | 1983-12-23 | Toa Nenryo Kogyo Kk | Production of catalytic component for olefin polymerization |
| JPS58222104A (en) * | 1982-06-21 | 1983-12-23 | Toa Nenryo Kogyo Kk | Catalytic component for olefin polymerization |
| FI75845C (en) * | 1986-04-01 | 1988-08-08 | Neste Oy | CATALYTIC COMPONENT FOR POLYMERING CATALYST AV ALFAOLEFINER OCH FOERFARANDE FOER DERAS FRAMSTAELLNING. |
| GB8708778D0 (en) * | 1987-04-13 | 1987-05-20 | Ici Plc | Particulate solid |
| IT1251462B (en) * | 1991-07-12 | 1995-05-15 | Enichem Polimeri | SOLID COMPONENT OF CATALYST FOR THE (CO) POLYMERIZATION OF ETHYLENE AND ALPHA OLEFINS. |
| CN101906017A (en) * | 2009-06-04 | 2010-12-08 | 中国石油化工股份有限公司 | Method for preparing alkoxyl magnesium solid particles |
| CN102453150B (en) * | 2010-10-25 | 2013-08-14 | 中国石油化工股份有限公司 | Support of olefinic polymerization catalyst and preparation method thereof, solid catalyst components for olefinic polymerization and olefinic polymerization catalyst |
| CN102838697B (en) * | 2011-06-24 | 2014-08-06 | 中国石油化工股份有限公司 | Catalyst component for high temperature olefin polymerization, and preparation method thereof |
| CN105713116B (en) * | 2014-12-03 | 2018-02-02 | 中国石油天然气股份有限公司 | Preparation method for the alkoxyl magnesium carrier of olefin polymerization catalysis |
| CN104356257B (en) * | 2014-12-03 | 2017-04-12 | 北京化工大学 | Preparation method and applications of alkoxyl magnesium carrier |
| CN105777951B (en) * | 2014-12-24 | 2018-10-16 | 中国石油天然气股份有限公司 | Alkoxyl magnesium carrier and preparation method thereof for olefin polymerization catalysis |
-
2018
- 2018-01-09 CN CN201810018038.XA patent/CN108102014B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477639A (en) * | 1983-05-27 | 1984-10-16 | Shell Oil Company | Olefin polymerization catalyst component and composition and method of preparation |
| JPS60110704A (en) * | 1983-11-22 | 1985-06-17 | Idemitsu Kosan Co Ltd | Production of polyolefin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108102014A (en) | 2018-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5038135B2 (en) | Spherical catalyst component for olefin polymerization and catalyst containing the same | |
| KR101582497B1 (en) | Spheroidal particles for olefin polymerization catalyst | |
| CN108250331B (en) | Composition, preparation method and application of olefin polymerization catalyst carrier | |
| KR102172790B1 (en) | Method for preparation of a catalyst component used for olefin polymerization | |
| CN111100218B (en) | Spherical alkoxy magnesium particles and preparation method thereof | |
| CN108219038B (en) | Composition of alkoxy magnesium particles and preparation method thereof | |
| CN111072803B (en) | Olefin polymerization catalyst carrier, preparation method and application thereof | |
| CN108017734B (en) | Components, preparation method and application of spherical alkoxy magnesium particles | |
| CN108191998B (en) | Components, preparation method and application of magnesium ethylate particles | |
| CN108102014B (en) | Components and preparation method of spherical alkoxy magnesium particles | |
| CN108084304B (en) | Components, preparation method and application of magnesium ethylate particles | |
| CN108102013B (en) | Composition of alkoxy magnesium particles and preparation method thereof | |
| KR100361086B1 (en) | Preparation method of catalyst for polymerization of ethylene | |
| CN108219039B (en) | Components and preparation method of spherical alkoxy magnesium particles | |
| CN108219040B (en) | Components, preparation method and application of spherical alkoxy magnesium particles | |
| CN108017735B (en) | Components and preparation method of spherical alkoxy magnesium particles | |
| CN107936154B (en) | Alkoxy magnesium catalyst carrier and preparation method and application thereof | |
| WO2012160574A2 (en) | Controlled morphology high activity polyolefin catalyst system | |
| JP4885130B2 (en) | Method for producing catalyst component for olefin polymerization | |
| CN102718901A (en) | Ultrahigh molecular weight polyethylene catalyst preparation method and catalyst prepared by same and application of catalyst | |
| KR101835745B1 (en) | Method of preparation of supporting particle | |
| CN117964805A (en) | Alkoxy magnesium catalyst carrier for olefin polymerization, preparation method thereof and solid catalyst for olefin polymerization | |
| KR100554269B1 (en) | A method for the preparation of a solid catalyst for alpha olefin polymerization | |
| KR100546506B1 (en) | A method for the preparation of a solid titanium catalyst for olefin polymerization | |
| CN107840914B (en) | Polyethylene catalyst component and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |