CN115925513A - Preparation method and application of spherical dialkoxy magnesium carrier - Google Patents
Preparation method and application of spherical dialkoxy magnesium carrier Download PDFInfo
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- CN115925513A CN115925513A CN202211468426.0A CN202211468426A CN115925513A CN 115925513 A CN115925513 A CN 115925513A CN 202211468426 A CN202211468426 A CN 202211468426A CN 115925513 A CN115925513 A CN 115925513A
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011777 magnesium Substances 0.000 title claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- -1 amide compound Chemical class 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- AZSQEXSKABOCGN-UHFFFAOYSA-M CC[Al+]CC.[Cl-].Cl.Cl.Cl Chemical compound CC[Al+]CC.[Cl-].Cl.Cl.Cl AZSQEXSKABOCGN-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HONQAQNYJBKAMA-UHFFFAOYSA-L magnesium;ethyl carbonate Chemical compound [Mg+2].CCOC([O-])=O.CCOC([O-])=O HONQAQNYJBKAMA-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the technical field of dialkoxy magnesium carrier preparation, and particularly relates to a preparation method and application of a spherical dialkoxy magnesium carrier. The method comprises the following steps: (1) Under the protection of inert gas, adding metal magnesium powder and alcohol serving as raw materials, halogen, an amide compound or an imide compound and alkali into a reactor, stirring, heating and carrying out reflux reaction; (2) And after hydrogen is completely discharged, continuously preserving the heat, cooling, washing and drying to obtain the dialkoxy magnesium carrier. The preparation method has simple and convenient process, does not need complex operation, has lower requirements on reaction equipment, and is suitable for amplification and industrial production. The reaction condition is mild, the cost of raw materials is low, and the use of expensive initiators is avoided.
Description
Technical Field
The invention belongs to the technical field of dialkoxy magnesium carrier preparation, and particularly relates to a preparation method and application of a spherical dialkoxy magnesium carrier.
Background
In the polypropylene industry, technological advances in catalysts play a very important role. The early catalysts for polymerizing olefin such as ethylene and propylene are represented by ferric chloride-ferric trichloride-diethyl aluminum chloride, and because the catalyst efficiency of the early catalysts in polypropylene polymerization is low, the long process flow and high energy consumption are caused by the fact that soluble random substances and residues in products are removed by a long and tedious post-treatment process. At the end of 1960 s, belgian Solvay company developed a titanium trichloride-isoamyl ether complex catalyst system, the catalytic activity of which is 3-5 times higher than that of the original catalyst, and the isotactic index of the product is effectively improved, but the complicated post-treatment process is still not solved.
Meanwhile, a supported catalyst appears, and the fact that magnesium chloride is a good carrier of the titanium trichloride active center is proved. On the basis, in 1980, japanese and Italian collaborate to develop an efficient catalyst, and a polypropylene product with an extremely high isotactic index can be obtained by using the catalyst.
Since the supported catalyst has incomparable advantages for olefin polymerization compared with other catalysts, the development of the catalyst has high industrial value and economic value.
The method of preparing a catalyst using magnesium dialkyl obtained by reacting metallic magnesium with alcohols as a carrier has recently become a research focus in the art because of the ability to secure a highly active catalyst and a polymer product having high stereoregularity, compared to other methods. However, in the case of using dialkoxy magnesium as a support, since the morphology and size distribution of dialkoxy magnesium particles and the apparent density directly affect the particle characteristics of a catalyst and a polymerization product, it is necessary to prepare a dialkoxy magnesium support having a uniform size and shape and a sufficiently high apparent density during the reaction of metallic magnesium with an alcohol. In particular, a large amount of large particle carriers causes deterioration in the flowability of the polymerization product, and it is difficult to meet the demand for industrial production.
Various methods for producing dialkoxy magnesium having a uniform shape have been disclosed in the prior art documents. US patent US 5162277 discloses the following process: carboxylating amorphous diethoxymagnesium with carbon dioxide to obtain magnesium ethylcarbonate, followed by recrystallization using various different or mixed solvents in the presence of additives to obtain a carrier having a size of 5 to 10 μm. The same concept and method is used in US 5955396. Japanese patent laid-open No. H06-87773 adopts the following method: and (3) carrying out spray drying on the diethoxymagnesium alcohol solution after carbon dioxide carboxylation. Then, decarboxylation reaction is carried out to prepare spherical particles. However, these methods have the disadvantages of complicated process, high process requirements, various raw materials used, and inability to provide a suitable carrier particle size and morphology as required.
Japanese patent laid-open Nos. H03-74341, 04-36891 and 08-73388 provide methods for synthesizing spherical or ellipsoidal diethoxymagnesium by reacting metallic magnesium with ethanol in the presence of iodine. However, in the production process, a large amount of reaction heat and hydrogen gas are generated, and since the reaction is rapid, it is difficult to control the reaction rate, and there is a problem that the diethoxymagnesium support obtained contains a large amount of fine particles or irregularly shaped large particles formed by agglomeration of multiple particles. Thus, when the catalyst prepared according to the method is used for olefin polymerization, excessive polymer particle size is caused, and the exothermic heat of polymerization generated during the polymerization destroys the particle shape, causing serious adverse consequences in the process. Meanwhile, the application effect of the carrier is also influenced by the presence of iodine.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a spherical dialkoxy magnesium carrier, which improves the catalytic reaction performance of olefin polymerization by adjusting the particle size and the shape of the dialkoxy magnesium carrier in a catalytic system in a polyolefin polymerization catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, the present invention provides a method for preparing a spherical dialkoxy magnesium support, the method comprising the steps of:
(1) Under the protection of inert gas, adding metal magnesium powder and alcohol serving as raw materials, halogen, an amide compound or an imide compound and alkali into a reactor, stirring, and heating for reflux reaction;
(2) And after hydrogen is completely discharged, continuously preserving the heat, cooling, washing and drying to obtain the dialkoxy magnesium carrier.
In the above technical solution, further, in the step (1), the halogen includes bromine or iodine.
In the above technical solution, further, in the step (1), the amide compound and the imide compound have the following general formulas i and ii, respectively:
wherein: r is alkyl, aryl, substituted alkyl, aryl, heterocycle or substituted heterocycle.
In the above technical means, further, in the step (1), the molar ratio of the amide or imide compound to the halogen is 1 (0.1 to 5.0).
In the above technical solution, further, in the step (1), the total mass of the amide or imide compound and the halogen is: mass =0.001 to 0.2 of metallic magnesium: 1. if the mass ratio is less than 0.001: at 1, the reaction rate is slow, e.g., greater than 0.2.
In the above technical solution, further, in the step (1), the alkali includes sodium hydroxide, potassium carbonate, piperazine, and diethylamine.
In the above technical solution, further, in the step (1), the molar ratio of the alkali to the halogen is 1 (0.002 to 5).
In the above-mentioned aspect, in the step (1), the particle diameter of the magnesium metal powder is 10 to 500 μm, preferably 50 to 200 μm. If the average particle diameter of the metal magnesium is less than 10 μm, the average particle diameter of the carrier to be produced is too fine to be used; if it exceeds 500. Mu.m, the average particle size of the resulting carrier becomes too large, and the morphology of the carrier is difficult to form a uniform spherical shape.
In the above technical solution, in the step (1), the alcohol is one or more of C1 to C6 aliphatic alcohols and aromatic alcohols, preferably one or more of methanol, ethanol and propanol, and most preferably ethanol; the aliphatic alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, and cyclohexanol.
In the above technical solution, further, in the step (1), the usage ratio of the magnesium metal to the alcohol is: the mass of the metal magnesium is that the volume of the alcohol is =1g, (5-50) ml, and preferably 1g, (7-20) ml. If the consumption of the alcohol is too small, the alcohol is difficult to stir uniformly; if the amount of the alcohol is too large, the surface of the particles becomes rough because the apparent density of the carrier of the product to be produced decreases.
In the above technical solution, in the step (1), the stirring speed is 50 to 300rpm/min, preferably 70 to 250rpm/min. If the stirring speed is out of this range, the particles will be non-uniform.
In the above technical solution, further, in the step (1), the reflux reaction temperature is 60 to 90 ℃, and the reflux reaction time is 0.5 to 20 hours, preferably 2 to 10 hours. When the temperature is lower than 60 ℃, the reaction speed is too slow; when the temperature is higher than 90 ℃, the reaction speed is too fast, the amount of fine particles increases, and a coagulation and agglomeration phenomenon occurs, and a uniform spherical carrier of a desired size cannot be obtained.
In the technical scheme, furthermore, the heat preservation time is 0.5-10 h, and then the temperature is reduced to 10-50 ℃.
In the above technical solution, further, in the step (2), one or more of alkanes and ethers are used for the washing.
In the above technical solution, further, in the step (2), the drying is performed for 0.5 to 10 hours under nitrogen.
In the above technical solution, further, the particle size of the dialkoxy magnesium carrier is 10 to 80 μm.
In another aspect, the present invention provides a use of the above dialkoxy magnesium support for a catalyst for olefin polymerization.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method has simple process, does not need complex operation, has lower requirement on reaction equipment, and is suitable for amplification and industrial production.
2. The reaction condition is mild, the cost of raw materials is low, and the use of expensive initiators is avoided.
3. The invention can obtain uniform spherical dialkoxy magnesium carrier particles with controllable particle size.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these specific embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
After a sufficient replacement with nitrogen gas was performed in a 5L glass reaction flask equipped with a stirrer, a heating mantle and a reflux condenser, 0.6g of acetamide, 1.6g of bromine, 0.2g of sodium hydroxide, 60g of magnesium metal (powder having an average particle size of 100 μm), and 800mL of anhydrous ethanol were charged, and the mixture was stirred at a stirring speed of 240rpm/min, and the reaction flask was heated to 78 ℃ to maintain ethanol reflux. After 5min of reaction, hydrogen was generated indicating initiation of the reaction. After all hydrogen is discharged, the reflux reaction is continued for 2h, the temperature is reduced to 50 ℃, and the mixture is washed for 3 times by using 2000mL of normal hexane. The washed product was dried under nitrogen for 24h to give 250g (88% yield) of a white powdery solid with good flowability.
The dried product was suspended in n-hexane and subjected to particle size measurement by a laser particle size analyzer by a light transmittance method, resulting in an average particle diameter of 20 μm.
Example 2
After a sufficient replacement with nitrogen gas was performed in a 5L glass reaction flask equipped with a stirrer, a heating mantle and a reflux condenser, 0.99g of succinimide, 1.59g of bromine, 0.2g of sodium hydroxide, 60g of metal magnesium (powder having an average particle size of 100 μm), and 800mL of anhydrous ethanol were put into the flask, and stirred at a stirring speed of 240rpm/min, and the reaction flask was heated to 78 ℃ to maintain the ethanol reflux. After 5min of reaction, hydrogen was generated indicating initiation of the reaction. After all hydrogen is discharged, the reflux reaction is continued for 2h, the temperature is reduced to 50 ℃, and the mixture is washed for 3 times by using 2000mL of normal hexane. The washed product was dried under nitrogen for 24h to yield 270g (95% yield) of a white powdery solid with good flowability.
The dried product was suspended in n-hexane and subjected to particle size measurement by a laser particle size analyzer by a light transmittance method, resulting in an average particle diameter of 25 μm.
The above examples are intended to be illustrative of the present invention and are not intended to limit the invention to these particular embodiments. Other variations and modifications within the spirit and scope of the invention and the appended claims will occur to persons skilled in the art and are intended to be covered by the invention.
Claims (10)
1. A method for preparing a spherical dialkoxy magnesium support, characterized in that it comprises the steps of:
(1) Under the protection of inert gas, adding metal magnesium powder and alcohol serving as raw materials, halogen, an amide compound or an imide compound and alkali into a reactor, stirring, and heating for reflux reaction;
(2) And after hydrogen is completely discharged, continuously preserving the heat, cooling, washing and drying to obtain the dialkoxy magnesium carrier.
2. The method according to claim 1, wherein in the step (1), the halogen comprises bromine or iodine;
the amide compound and the imide compound respectively have the following general formulas I and II:
wherein: r is alkyl, aryl, substituted alkyl, aryl, heterocycle or substituted heterocycle;
the molar ratio of the amide or imide compound to the halogen is 1 (0.1-5.0); the total mass of the amide or imide compound and the halogen is as follows: mass =0.001 to 0.2 of metallic magnesium: 1.
3. the method according to claim 1, wherein in the step (1), the base comprises sodium hydroxide, potassium carbonate, piperazine, diethylamine;
the molar ratio of the alkali to the halogen is 1 (0.002-5).
4. The production method according to claim 1, wherein the metallic magnesium powder has a particle size of 10 to 500 μm;
the alcohol is one or more of C1-C6 aliphatic alcohol and aromatic alcohol; the aliphatic alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, and cyclohexanol;
the dosage ratio of the metal magnesium to the alcohol is as follows: the mass of the metal magnesium is that the volume of the alcohol is =1g (5-50) ml.
5. The production method according to claim 1, wherein in the step (1), the stirring speed is 50 to 300rpm/min;
the reflux reaction temperature is 60-90 ℃, and the reflux reaction time is 0.5-20 h.
6. The preparation method according to claim 1, wherein in the step (2), the heat preservation time is 0.5-10 h, and then the temperature is reduced to 10-50 ℃.
7. The method according to claim 1, wherein in step (2), one or more of alkanes and ethers are used for washing.
8. The method according to claim 1, wherein in the step (2), the drying is performed under nitrogen for 0.5 to 10 hours.
9. The method according to claim 1, wherein the dialkoxy magnesium support has a particle size of 10 to 80 μm.
10. Use of a dialkoxy magnesium support according to any one of claims 1 to 9 for a support for an olefin polymerization catalyst.
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| CN110483247A (en) * | 2019-07-16 | 2019-11-22 | 北京国达恒泰科贸有限责任公司 | Metal alkoxides powder and preparation method and application |
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2022
- 2022-11-22 CN CN202211468426.0A patent/CN115925513A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084196A (en) * | 2004-08-16 | 2007-12-05 | 雅宝公司 | Process for producing n-halogenated organic compounds |
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