Supported polymetal olefin polymerization catalyst, preparation method and use thereof

Patent metadata

Field	Value
Publication number	US-10053523-B2
Application number	US-201515535902-A
Country	US
Kind code	B2
Filing date	Nov 25, 2015
Priority date	Dec 16, 2014
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

The present invention relates to a supported polymetal olefin polymerization catalyst, comprising a porous support, a magnesium-containing support component, a transition metal titanium component supported on the porous support, and further comprising at least one non-magnesium metal component supported on the porous support. Further provided is a preparation method and a use of the supported polymetal olefin polymerization catalyst. An efficient composite support supported polymetal Ziegler-Natta catalyst is provided in the present invention, wherein a porous support, a soluble magnesium compound, and a soluble non-magnesium metal compound are used as raw materials. The supporting of titanium is achieved while a composite support containing magnesium and non-magnesium metal components is formed in situ in the surface of the porous support. The present invention has the advantage of a simple preparation method, a low cost, a controllability of morphology, properties of the catalyst, etc. Comparing the provided catalyst with the same type of magnesium/titanium catalyst free of non-magnesium metal components, the catalytic performance such as polymerization activity, hydrogen regulation sensitivity and copolymerization performance are significantly improved.

First claim

What is claimed is:

1. A supported polymetal olefin polymerization catalyst, comprising: a porous support; a magnesium-containing support component; a transition metal titanium component supported on the porous support; and further comprising at least one non-magnesium metal component supported on the porous support, wherein the non-magnesium metal component comprises a metal other than magnesium selected from the group consisting of vanadium, chromium, titanium, ferrum, cobalt, nickel, copper, zinc, molybdenum, wolframium, zirconium, aluminum, lithium, sodium, potassium, calcium, and combinations thereof, and wherein the general formula of the non-magnesium metal component is M d O f (L 2 ) e , wherein M is the non-magnesium metal, L 2 is a C 1 -C 20 alkyl group R 2 or alkoxy group R 2 O, wherein R 2 is a saturated or unsaturated straight-chain, branched or cyclic chain (including aromatic hydrocarbons), 1≤d≤2, 0≤f≤5, 0≤e≤5, and wherein when e is 2 or more than 2, each R 2 may be the same or different.

2. The supported polymetal olefin polymerization catalyst according to claim 1 , wherein said magnesium-containing support component is a magnesium compound and is one or more of the general formula MgO v (L 1 ) j Cl m and combinations thereof, wherein L 1 is a C 1 -C 20 alkyl group R 1 or alkoxy group R 1 O, wherein R 1 is a saturated or unsaturated straight-chain, branched or cyclic chain (including aromatic hydrocarbons), 0≤v≤1, 0≤m≤2, 0≤j≤2, and wherein when j is 2, L 1 may be the same or different.

3. The supported polymetal olefin polymerization catalyst according to claim 1 , wherein the transition metal titanium component is a titanium-containing compound having the general formula Ti(L 3 ) n Cl 4-n , or Ti(L 3 ) g Cl 3-g , wherein L 3 is a C 1 -C 20 alkyl group R 3 or alkoxy group R 3 O, wherein R 3 is a saturated or unsaturated straight-chain, branched or cyclic chain (including aromatic hydrocarbons), 1≤n≤4, 0≤g≤3, and wherein when n or g is 2 or more than 2, each R 3 may be same or different.

4. The supported polymetal olefin polymerization catalyst according to claim 1 , wherein the weight of magnesium of the magnesium-containing support component is 0.5 wt % to 20 wt % based on the total weight of the catalyst.

5. The supported polymetal olefin polymerization catalyst according to claim 1 , wherein the molar ratio of the transition metal titanium component to the magnesium-containing support component is 0.01:1 to 10:1.

6. The supported polymetal olefin polymerization catalyst according to claim 1 , wherein the molar ratio of the magnesium-containing support component to the non-magnesium metal component is 0.1:1 to 30:1.

7. A preparation method of the supported polymetal olefin polymerization catalyst according to claim 1 comprising: a step S1, wherein the porous support (carrier) is impregnated with a mixed solution of a soluble magnesium compound and non-magnesium metal compound, followed by calcination at high temperature of 300˜900° C.; and a step S2, wherein the product obtained from step S1 further reacts with the transition metal titanium component or solution thereof to obtain the catalyst.

8. The preparation method of the supported polymetal olefin polymerization catalyst according to claim 7 wherein step S1 further comprises modifying the surface of the calcined product after calcination reaction at high temperature using one or two of an organic magnesium compound and an organic aluminum compound to remove the surface residual hydroxyl group, wherein the general formula of the organic magnesium compound is R 5 p MgX 2-p , wherein R 5 is a C 1 -C 20 alkyl group, R 5 is a saturated or unsaturated straight-chain, branched or cyclic chain (including aromatic hydrocarbons), 0≤p≤2, wherein when p=2, R 5 may be same or different, and wherein X is one or more halogens selected from the group consisting of fluorine, chlorine, bromine and iodine.

9. The preparation method of the supported polymetal olefin polymerization catalyst according to claim 7 wherein the soluble magnesium compound is magnesium nitrate, magnesium acetate, magnesium bicarbonate, magnesium chromate, magnesium fluoride, magnesium sulfate, magnesium chlorate or magnesium phosphate.

10. A method of preparing a supported polymetal olefin polymerization catalyst comprising: a porous support; a magnesium-containing support component; a transition metal titanium component supported on the porous support; and further comprising at least one non-magnesium metal component supported on the porous support, the method comprising: a step S1, wherein the porous support (carrier) is impregnated with a mixed solution of a soluble magnesium compound and non-magnesium metal compound, followed by calcination at high temperature of 300˜900° C.; and a step S2, wherein the product obtained from step S1 further reacts with the transition metal titanium component or solution thereof to obtain the catalyst, wherein the soluble non-magnesium metal compound is selected from:
one or more than one soluble vanadium compounds of ammonium hexafluorovanadate, vanadium nitrate, vanadium oxyoxalate, ammonium metavanadate, vanadyl sulfate, vanadium(IV) sulfate oxide hydrate, vanadyl(III)sulfate, vanadium trichloride, sodium orthovanadate, sodium metavanadate, vanadylacetonate vanadium oxide, isopropyl orthovanadate, vanadyl-tris-n-propoxide, vanadyl acetylacetonate, vanadium oxytriethoxide, vanadyl chloride, and vanadium silicide;
one or more than one soluble chromium compounds of chromic nitrate, chromium chloride, chromic sulfate, diammonium chromate, ammonium bichromate, and chromic acetate;
one or more than one soluble molybdenum compounds of molybdenum phosphate, molybdenum acetate, molybdenum sulfate, silicomolybdic acid, ammonium molybdate, and molybdenum nitride;
one or more than one soluble wolframium compounds of wolframium nitrate, phosphotungstic acid, wolframium sulfate, wolframium carbonate, and wolframium acetate one or more than one soluble aluminum compounds of aluminum nitrate, aluminum sulfate, aluminum oxalate and aluminum borate;
one or more than one soluble zirconium compounds of zirconium nitrate, zirconium carbonate, zirconium oxysulfate and basic zirconium sulfate;
one or more than one soluble zinc compounds of zinc nitrate, zinc oxalate, zinc thiolacetic, zinc acetate and zinc carbonate hydroxide;
one or more than one soluble copper compounds of copper sulfate, copper carbonate, cupric nitrate and copper phosphate;
one or more than one soluble ferric compounds of ferric acetate, ferric nitrate, ferric oxalate, and ferric gluconate; and
one or more than one soluble nickel compounds of nickel nitrate, nickel sulfate, nickel carbonate and chromic acetate.

11. The preparation method of the supported polymetal olefin polymerization catalyst according to claim 7 , wherein the titanium-containing component is one or more of the general formula Ti(L 4 ) h Cl 4-h or Ti(L 4 ) s Cl 3-s or Ti(L 4 ) t Cl 2-t , wherein, L 4 is a C 1 -C 20 alkyl group R 4 or alkyl oxide group R 4 O, wherein R 4 is a saturated or unsaturated straight-chain, branched or cyclic chain (including aromatic hydrocarbons), 0≤h≤4, 0≤s≤3, 0≤t≤2, and wherein when h or s is 2 or more than 2 or t is 2, R 4 may be the same or different.

12. A method of using a supported polymetal olefin polymerization catalyst according to claim 1 , comprising contacting the supported polymetal olefin polymerization catalyst with one or more reactants selected from the group consisting of ethylene, propylene, butene, hexene and octene, whereby the one or more reactants are polymerized or copolymerized.

Assignees

• Univ East China Science & Tech

Inventors

• Liu Boping
• Wang Jingwen
• Cheng Ruihua
• He Xuelian
• Liu Zhen
• Zhao Ning

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title