CN115975080B - Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method - Google Patents
Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method Download PDFInfo
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Abstract
The invention belongs to the technical field of ethylene polymerization, and discloses a magnesium-containing titanium catalyst component for ethylene polymerization, a catalyst and an ethylene polymerization reaction method, wherein the preparation method of the magnesium-containing titanium catalyst component comprises the following steps: 1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at a reaction temperature of 95-110 ℃ to obtain a uniform solution; 2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, and washing and drying to obtain the magnesium-containing titanium catalyst component. The polymer prepared by the catalyst has obviously higher bulk density and particle sphericity.
Description
Technical Field
The invention belongs to the technical field of ethylene polymerization, and in particular relates to a magnesium-titanium-containing catalyst component and catalyst for ethylene polymerization and an ethylene polymerization reaction method.
Background
In the polymerization of olefins, particularly the polymerization of ethylene or the copolymerization of ethylene with alpha-olefins, catalyst components based on magnesium, titanium, halogen and electron donors are mostly used.
In practice, the above catalyst component is mainly composed of magnesium chloride, titanium chloride and an electron donor. The early catalyst component is prepared by mixing and grinding magnesium chloride, titanium tetrachloride and an electron donor together, the catalyst has low activity, the prepared polymer has wide particle size distribution, and coarse powder and fine powder are more, so that the catalyst is basically eliminated.
One is to support the catalyst component on porous spherical silica gel in a fixed form, and as disclosed in patent document CN1158136, a main catalyst for producing ethylene high polymer, the main catalyst comprising an inorganic carrier (preferably an active silica carrier), a chlorine compound supported on the carrier, a magnesium compound supported on the carrier, and a titanium compound supported on the carrier. The main catalyst is characterized in that: the catalyst particles are spherical, have better fluidity and good hydrogen regulation sensitivity, and the polymerization activity is less reduced along with the increase of the addition amount of the chain transfer agent (hydrogen), so that the catalyst is suitable for producing polyethylene resin with wide molecular weight distribution.
The other is to dissolve a magnesium compound into a uniform solution, and then to separate out magnesium chloride particles by reacting with a titanium compound while supporting titanium chloride and an electron donor, as disclosed in patent documents CN85100997, CN1112373C, CN1229092A, CN1958620, etc. The method generally dissolves the magnesium compound in the polar solvent, and separates out the catalyst component particles containing titanium magnesium and electron donor through the contact reaction of the dissolution liquid and titanium tetrachloride, the method is simple and easy to implement, and the performance of the catalyst component is better than that of the mixed and ground catalyst.
In patent document CN85100997, magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution, and then reacted with at least one precipitation aid, a halide of transition metal titanium, and a derivative thereof. Because the organic epoxy compound and the organic phosphorus compound which do not contain active hydrogen are adopted as solvents, the dissolution of magnesium chloride is slower, the reaction of the magnesium chloride and titanium tetrachloride is convenient to control, so that the precipitated particles are better in particle shape, are similar to spheres, the prepared polymer is better in particle shape and higher in stacking density, but the prepared catalyst component is lower in activity, and the ash content in the product is particularly high when the catalyst component is applied to industrial production.
In patent document CN1112373C, magnesium chloride is dissolved in isooctanol using decane as a dispersant, and silane is added as a precipitating agent, and catalyst component particles are precipitated by reaction with titanium tetrachloride. The solvent used in the system is isooctyl alcohol, the raw material is simple, the catalyst component has higher activity and better hydrogen regulation performance in ethylene polymerization, but the preparation method of the catalyst component uses more titanium tetrachloride, and the particle shape of the catalyst component is similar to sphere and is not regular.
Patent document CN1229092a discloses a catalyst for ethylene polymerization or copolymerization, which is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound, adding a low-carbon alcohol as an electron donor activator to form a uniform solution, and reacting with at least one anhydride-type precipitation aid, a halide of transition metal titanium and its derivatives, and shows high activity when used for slurry polymerization of ethylene, but the morphology and particle size distribution of the catalyst component prepared by the method still need to be improved.
In patent document CN1958620, a catalyst is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound and a low carbon alcohol to form a uniform solution, and then reacting with at least one silane compound and a halide of transition metal titanium and its derivative, and the catalyst has high activity when used for slurry polymerization of ethylene, but the morphology and particle size distribution of the catalyst component prepared by this method still need to be improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a magnesium-titanium-containing catalyst component for ethylene polymerization, a catalyst and an ethylene polymerization method, wherein the polymer prepared by the catalyst has high bulk density and high particle sphericity, and the surface of the polymer is smoother.
The first aspect of the present invention provides a magnesium-containing titanium catalyst component for ethylene polymerization, the preparation method of the magnesium-containing titanium catalyst component comprising:
1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at a reaction temperature of 95-110 ℃ to obtain a uniform solution;
2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, and washing and drying to obtain the magnesium-containing titanium catalyst component.
In a second aspect the present invention provides a catalyst for the polymerization of ethylene comprising the magnesium-containing titanium catalyst component described above, and an organoaluminum compound.
In a third aspect of the present invention, there is provided a process for the polymerization of ethylene comprising: ethylene or ethylene and alpha-olefin are reacted in the presence of the catalyst described above.
According to the invention, the magnesium compound is dissolved in a solvent system containing the organic phosphorus compound, the organic alcohol compound and the diluent, the temperature during dissolution is controlled, the activity of the obtained catalyst is normal, the molecular weight of the prepared polymer is equivalent, the bulk density and the particle sphericity of the polymer are obviously improved, the surface of the polymer is smoother, and the protrusions are less. The catalyst component of the invention has simple preparation materials and can still obtain the catalyst with better performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an electron micrograph of the polymer produced in example 1.
FIG. 2 is an electron micrograph of the polymer produced in the comparative example.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention, there is provided a magnesium-containing titanium catalyst component for ethylene polymerization, the magnesium-containing titanium catalyst component comprising:
1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at a reaction temperature of 95-110 ℃ to obtain a uniform solution;
2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, and washing and drying to obtain the magnesium-containing titanium catalyst component.
In the present invention, the magnesium compound may employ a magnesium-containing compound known to those skilled in the art, such as a halide of magnesium, an alkoxide of magnesium, a halogenated alkoxide of magnesium, or the like. Preferably, the magnesium compound is magnesium dihalide or a derivative in which one halogen atom in the formula of magnesium dihalide is replaced by a hydrocarbon group or a haloalkoxy group.
According to the present invention, the organophosphorus compound may be selected from hydrocarbyl or halocarbyl esters of orthophosphoric acid, hydrocarbyl or halocarbyl esters of phosphorous acid. For example, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite and the like.
According to the present invention, the organic alcohol compound may be selected from linear alcohols having 1 to 8 carbon atoms or isomeric alcohols. Specific examples of the organic alcohol compound include, but are not limited to: at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol and isooctanol. Preference is given to straight-chain alcohols or isomeric alcohols having 3 to 8 carbon atoms.
In the present invention, the diluent may be benzene, toluene, xylene, chlorobenzene or a derivative thereof.
According to the invention, the titanium compound has the general formula Ti (OR) aXb, wherein R is an aliphatic OR aromatic hydrocarbon radical of C 1-C14, X is a halogen atom, a is an integer from 0 to 2, b is an integer from 0 to 4, a+b=3 OR 4.
Specifically, the titanium compound may be at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxide and titanium trichloride. The titanium compound is preferably titanium tetrachloride, titanium trichloro-monoethoxy or titanium trichloride.
According to the present invention, the organophosphorus compound is present in an amount of 0.01 to 10 moles, preferably 0.02 to 4 moles, per mole of the magnesium compound; the organic alcohol compound is used in an amount of 0.01 to 15 moles, preferably 0.05 to 10 moles; the dosage of the diluent is 0.2-5L; the titanium compound is used in an amount of 0.2 to 30 moles, preferably 1 to 20 moles.
Preferably, in step 1), the stirring speed is 350-500rpm and the reaction time is 0.5-1.5h.
Preferably, in step 2), the homogeneous solution is cooled to-30 ℃ to 5 ℃ and the temperature of the heating is 60-110 ℃.
According to a second aspect of the present invention there is provided a catalyst for the polymerization of ethylene comprising the magnesium-containing titanium catalyst component described above, and an organoaluminum compound.
In the invention, the general formula of the organic aluminum compound can be AlR 1 nX3-n, wherein R 1 is hydrogen, and the alkyl, aralkyl or aryl of which the carbon number is 1-20 is preferred; x is halogen, preferably chlorine or bromine; n is a number of 0 < n.ltoreq.3.
In particular, the organoaluminum compound may be trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, preferably triethylaluminum triisobutylaluminum.
The molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-containing titanium catalyst component is 5-5000:1, preferably 20-500:1.
According to a third aspect of the present invention, there is provided a process for the polymerisation of ethylene comprising: ethylene or ethylene and alpha-olefin are reacted in the presence of the catalyst described above.
The ethylene polymerization of the present invention is carried out in a slurry state, and the solvent may be a linear or branched alkane such as hexane, heptane, octane, decane or a derivative thereof, etc.
The reaction conditions include: the reaction pressure is 0.05-10Mpa, preferably 0.1-5Mpa; the reaction temperature is 30-120 ℃, preferably 40-90 ℃, when the temperature is too high, ethylene molecules are easy to undergo free radical polymerization, the molecular weight of the prepared polyethylene is not high, and when the temperature is too low, the catalyst activity is low or the polyethylene is not polymerized; the reaction time is 1.5 to 10 hours, preferably 1.5 to 2.5 hours.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
In the following examples and comparative examples:
particle size distribution of the catalyst component: mastersizer 2000 instrument, malvern, uk;
polymer apparent Bulk Density (BD): measured with reference to ASTM D1895-96;
polymer molecular weight (Mw): a viscosity method;
polymer sphericity: CAMSIZER particle analyzer;
description: the particles were spherical when the sphericity was 1, and the smaller the sphericity, the more irregular the particle shape.
Examples 1-4 illustrate magnesium-containing titanium catalyst components and catalysts of the present invention and ethylene polymerization.
Example 1
Adding 4.8 g of magnesium chloride, 110 ml of toluene, 5.0 ml of tributyl phosphate and 11.6 ml of n-butyl alcohol into a reaction kettle, reacting for 1 hour at the stirring speed of 450rpm and the temperature of 103 ℃, cooling to-10 ℃, dropwise adding 36 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene and 60 ℃, washing for 4 times with organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Polymerization of ethylene: the 2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 2 mg of a magnesium-containing titanium catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and sphericity were determined. The polymer photograph is shown in FIG. 1.
Example 2
Adding 4.8 g of magnesium chloride, 100 ml of toluene, 6.0 ml of tributyl phosphate and 8.4 ml of n-propanol into a reaction kettle, reacting for 1 hour at the temperature of 103 ℃ at the stirring speed of 450rpm, cooling to-10 ℃, dropwise adding 36 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing for 4 times with organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Polymerization of ethylene: as in example 1.
Example 3
Adding 4.8 g of magnesium chloride, 90 ml of toluene, 6.0 ml of tributyl phosphate and 9.2 ml of n-butyl alcohol into a reaction kettle, reacting for 1 hour at the stirring rotation speed of 450rpm and the temperature of 103 ℃, cooling to-10 ℃, dropwise adding 40 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene and 60 ℃, washing for 4 times with organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Polymerization of ethylene: as in example 1.
Example 4
The magnesium-titanium-containing catalyst component was prepared differently from example 1 in that titanium tetrachloride was added dropwise while cooling to-20 ℃.
Polymerization of ethylene: as in example 1.
Comparative example 1
Adding 4.8 g of magnesium chloride, 55 ml of toluene, 3.0 ml of epichlorohydrin, 3.6 ml of tributyl phosphate and 7.6 ml of ethanol into a reaction kettle, reacting for 1 hour at the stirring speed of 450rpm and the temperature of 55 ℃, adding 0.8 g of phthalic anhydride, keeping the temperature of 55 ℃ for 1 hour, cooling to-30 ℃, dropwise adding 40ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, keeping the temperature for 1.0 hour, washing twice with 120 ml of toluene at 60 ℃, washing for 4 times with hexane as an organic solvent, and drying to obtain the catalyst component. The polymer photograph is shown in FIG. 2.
Polymerization of ethylene: the catalyst component was added in an amount of 10 mg as in example 1.
Comparative example 2
4.8 G of magnesium chloride, 110 ml of toluene, 5.0 ml of tributyl phosphate and 11.6 ml of n-butanol are added into a reaction kettle, and the reaction is carried out for 1 hour under the conditions of stirring rotation speed of 450rpm and temperature of 55 ℃, so that the dissolution is incomplete and the system is turbid. Cooling to-10 ℃, dropwise adding 36 ml of titanium tetrachloride, heating to 80 ℃ within 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing 4 times with hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Polymerization of ethylene: the catalyst component was added in an amount of 10 mg as in example 1.
The catalyst activities and polymer properties of each example and comparative example are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst of the present invention was normal in activity, and the molecular weight of the prepared polymer was comparable, and the bulk density and the sphericity of the particles of the polymer were significantly higher, as compared with the comparative catalyst. Comparing fig. 1 and 2, it can be seen that the polymer prepared with the catalyst component of the present invention has a smoother surface and fewer protrusions.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (19)
1. A magnesium-titanium-containing catalyst component for ethylene polymerization, characterized in that the preparation method of the magnesium-titanium-containing catalyst component comprises the following steps:
1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at a reaction temperature of 95-110 ℃ to obtain a uniform solution;
2) Cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, and washing and drying to obtain the magnesium-containing titanium catalyst component;
The diluent is benzene, toluene, xylene, chlorobenzene or derivatives thereof.
2. The magnesium-titanium-containing catalyst component for ethylene polymerization according to claim 1, wherein the magnesium compound is magnesium dihalide or a derivative in which one halogen atom in the formula of magnesium dihalide is replaced with a hydrocarbon group or a halogen hydrocarbyloxy group.
3. The magnesium-titanium containing catalyst component for ethylene polymerization according to claim 1, wherein the organic phosphorus compound is selected from hydrocarbyl or halogenated hydrocarbyl esters of orthophosphoric acid, hydrocarbyl or halogenated hydrocarbyl esters of phosphorous acid.
4. The magnesium-containing titanium catalyst component for ethylene polymerization according to claim 3, wherein the organic phosphorus compound is trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite.
5. The magnesium-titanium containing catalyst component for ethylene polymerization according to claim 1, wherein the organic alcohol compound is selected from a linear alcohol having 1 to 8 carbon atoms or an isomeric alcohol.
6. The magnesium-containing titanium catalyst component for ethylene polymerization according to claim 5, wherein the organic alcohol compound is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol and isooctanol.
7. The magnesium-containing titanium catalyst component for ethylene polymerization according to claim 1, wherein the titanium compound has a general formula of Ti (OR) aXb, wherein R is an aliphatic hydrocarbon group OR an aromatic hydrocarbon group of C 1-C14, X is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, a+b=3 OR 4.
8. The magnesium-containing titanium catalyst component for ethylene polymerization according to claim 7, wherein the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium chlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy and titanium trichloride.
9. The magnesium containing titanium catalyst component for ethylene polymerization according to claim 8, wherein the titanium compound is titanium tetrachloride, titanium trichloro-monoethoxy or titanium trichloride.
10. The magnesium-titanium-containing catalyst component for ethylene polymerization according to claim 1, wherein the organophosphorus compound is 0.01 to 10 moles per mole of magnesium compound; the organic alcohol compound is used in an amount of 0.01 to 15 mol; the dosage of the diluent is 0.2-5L; the titanium compound is used in an amount of 0.2 to 30 moles.
11. The magnesium-titanium-containing catalyst component for ethylene polymerization according to claim 10, wherein the organic phosphorus compound is 0.02 to 4 moles per mole of magnesium compound; the organic alcohol compound is used in an amount of 0.05 to 10 mol; the dosage of the diluent is 0.2-5L; the titanium compound is used in an amount of 1 to 20 moles.
12. The magnesium-titanium containing catalyst component for ethylene polymerization according to claim 1, wherein in the step 1), the stirring speed is 350 to 500rpm and the reaction time is 0.5 to 1.5 hours;
in the step 2), the uniform solution is cooled to the temperature of minus 30 ℃ to 0 ℃ and the temperature of the uniform solution is raised to 60 ℃ to 110 ℃.
13. A catalyst for ethylene polymerization, characterized in that it comprises the magnesium-containing titanium catalyst component according to any one of claims 1 to 12, and an organoaluminum compound;
the molar ratio of aluminum in the organic aluminum compound to titanium in the magnesium-containing titanium catalyst component is 5-5000:1.
14. The catalyst for ethylene polymerization according to claim 13, wherein the organoaluminum compound has the general formula AlR 1 nX3-n, wherein R 1 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group or an aryl group; x is chlorine or bromine; n is 0<n.ltoreq.3.
15. The catalyst for ethylene polymerization according to claim 14, wherein the organoaluminum compound is trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride.
16. The catalyst for ethylene polymerization according to claim 15, wherein the organoaluminum compound is triethylaluminum, triisobutylaluminum.
17. The catalyst for ethylene polymerization according to claim 13, wherein the molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-containing titanium catalyst component is 20-500:1.
18. A method for polymerizing ethylene, characterized in that, the ethylene polymerization process comprises: reacting ethylene or ethylene with an alpha-olefin in the presence of the catalyst of any one of claims 13-17;
the reaction conditions include: the pressure of the reaction is 0.05-10Mpa; the reaction temperature is 30-120 ℃; the reaction time is 1.5-10h.
19. The ethylene polymerization process of claim 18, wherein the reaction conditions comprise: the pressure of the reaction is 0.1-5Mpa; the reaction temperature is 40-90 ℃; the reaction time is 1.5-2.5h.
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| CN101353385A (en) * | 2008-09-27 | 2009-01-28 | 北京化工大学 | Catalyst for ethylene polymerization or copolymerization and its preparation method |
| CN103059171B (en) * | 2011-10-18 | 2015-06-17 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization |
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| CN108084305B (en) * | 2016-11-22 | 2020-12-01 | 中国石油天然气股份有限公司 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
| CN112625154B (en) * | 2019-10-09 | 2023-07-21 | 中国石油化工股份有限公司 | Titanium catalyst component for olefin polymerization, preparation method thereof, catalyst containing titanium catalyst component and application of titanium catalyst component |
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