CN112679634A - Solid metallocene catalyst and application thereof - Google Patents
Solid metallocene catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a solid metallocene catalyst, which is a reaction product of solid aluminoxane and a metallocene compound. The molar ratio of the solid aluminoxane to the metallocene compound is (10-2000): 1, preferably (20-500): 1. the solid aluminoxane is prepared by the following method: dissolving aluminoxane in an organic solvent, and then removing trimethylaluminum in the organic solvent to obtain aluminoxane powder; and (3) carrying out molding treatment on the aluminoxane powder in an organic solvent to obtain solid aluminoxane. The invention does not adopt an inert carrier to load the metallocene active component, but leads the aluminoxane to be solidified so as to load the metallocene active component; compared with the traditional supported metallocene catalyst, the catalyst has more uniform active center, higher loading capacity and better performance. When the catalyst is used in olefin polymerization reaction, the performance is good, and the polymerization activity is obviously improved.
Description
Technical Field
The invention relates to a metallocene catalyst and application of the solid metallocene catalyst in olefin polymerization, belonging to the field of olefin polymerization.
Background
In the field of olefin polymerization, metallocene catalysts are referred to as homogeneous catalyst systems, i.e., metallocene compounds form active components with cocatalysts (methylaluminoxane (MAO) or cationizing compounds capable of forming cationic active centers of the metallocene compounds such as borates, etc.) to catalyze olefin polymerization, and the systems can be industrially used in homogeneous polymerization systems such as solution polymerization systems. When the metallocene catalyst is applied to a slurry or gas phase polymerization process, in order to ensure the long-period stable operation of a device, the polymer needs to be ensured to have good particle morphology, namely, a metallocene active center needs to be loaded on an inert carrier to form a solid catalyst, and then the solid catalyst can be successfully applied to industrial production, but the supported catalyst also has the defects that the distribution of the catalyst active center is possibly uneven, the molecular weight distribution of the polymer is widened and the like; moreover, since MAO itself is a mixture, oligomers having active groups and free Trimethylaluminum (TMA) that is not involved in the reaction exist, which may cause sheeting or reactor fouling during the polymerization process, affecting the long-term operation of the reactor; meanwhile, the content of the active components loaded on each gram of the catalyst is reduced due to the addition of the inert carrier, and the activity of the catalyst is reduced. In the field of homogeneous polymerization, a relatively large MAO/metallocene ratio is required, in which case only homogeneous MAO systems can be used.
Methylaluminoxane (MAO) is generally prepared by partial hydrolysis of trimethylaluminum in toluene solvent, and in some polymer applications, such as in the food packaging field, toluene residues cannot be present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a solid metallocene catalyst and application thereof, wherein an inert carrier is not adopted to load a metallocene active component, but aluminoxane is solidified to further load the metallocene active component; compared with the traditional supported metallocene catalyst, the catalyst has more uniform active center, higher loading capacity and better performance. When the catalyst is used in olefin polymerization reaction, the performance is good, and the polymerization activity is obviously improved.
According to one aspect of the present invention, there is provided a solid metallocene catalyst which is a reaction product of a solid aluminoxane and a metallocene compound.
According to some embodiments of the invention, the molar ratio m (Al: Zr) of the solid aluminoxane to the metallocene compound is (10-2000): 1, preferably (20-500): 1.
according to a preferred embodiment of the present invention, the solid aluminoxane is prepared by the following method:
removing trimethylaluminum in the aluminoxane to obtain aluminoxane powder;
and (3) carrying out molding treatment on the aluminoxane powder in an organic solvent to obtain solid aluminoxane.
According to a preferred embodiment of the present invention, the solid aluminoxane has a particle size of from 5 to 50 μm, preferably from 5 to 30 μm.
According to some embodiments of the present invention, the solid aluminoxane is prepared by the following method:
(1) dissolving aluminoxane in a solvent A, and then carrying out vacuum drying treatment on the obtained solution to remove trimethylaluminum in the solution to obtain aluminoxane powder;
(2) and dissolving the aluminoxane powder by using a solvent A, reacting for a period of time at a certain temperature, adding a solvent B, separating out a solid, and washing and drying to obtain the solid aluminoxane.
According to a preferred embodiment of the present invention, the organic solvent a may be an aromatic hydrocarbon or an aliphatic hydrocarbon, and may be one or more of toluene, benzene, xylene, pentane, n-hexane, cyclohexane, methylcyclohexane, heptane, and isoparaffin thereof.
According to a preferred embodiment of the present invention, the organic solvent B may be an aromatic hydrocarbon or an aliphatic hydrocarbon, and may be one or more of toluene, benzene, xylene, pentane, n-hexane, cyclohexane, methylcyclohexane, heptane, and isoparaffin thereof.
According to a preferred embodiment of the invention, in the step (2), the aluminoxane powder is dissolved by using a solvent A, the temperature is raised to 80-110 ℃, the reaction is carried out for 0.5-15 hours under stirring, a solvent B is added, a solid is precipitated, and the solid aluminoxane is obtained after washing and drying.
According to a preferred embodiment of the present invention, a toluene solution of aluminoxane is stirred at 50 ℃ and dried under vacuum to be subjected to a trimethylaluminum removal treatment, thereby obtaining a solid aluminoxane powder. Then, the aluminoxane powder is dissolved in toluene to form a solution, and the content of the aluminoxane in the solution is generally 5 to 40%. And the solution was heated to 100 ℃ and reacted for 10 hours with stirring. Adding normal hexane, settling, filtering, washing and drying to obtain the solid aluminoxane.
According to some preferred embodiments of the invention, the aluminoxane has the general formula:
in the formulae I and II, R1-R4Are identical or different from each other and are selected from C1-C12Preferably methyl; a is an integer of 4 to 30, preferably an integer of 10 to 30.
According to some embodiments of the invention, the aluminoxane is preferably Methylaluminoxane (MAO) and modified methylaluminoxane, preferably methylaluminoxane.
According to some embodiments of the invention, the metallocene compound has the general structural formula Cp 'X Cp' MQ2(ii) a Wherein Cp 'and Cp' which may be the same or different, are cyclopentadienylene derivative groups, preferably selected from the group consisting of substituted or unsubstituted cyclopentadienyl groups, substituted or unsubstituted indenyl groups and substituted or unsubstituted fluorenyl groups, more preferably substituted or unsubstituted indenyl groups;
when the Cp 'and Cp' contain substituents,the substituent is selected from C1-C12Is preferably selected from C1-C12One or more of alkyl groups of (a), more preferably one or more selected from methyl, ethyl, propyl, isopropyl, butyl and isobutyl;
x is selected from C1-C4Preferably an ethylene bridge;
said M is selected from group IVB elements, preferably Zr and/or Ti, most preferably Zr;
q is selected from halogen, preferably chlorine.
In a preferred embodiment of the present invention, examples of the metallocene compound include, but are not limited to: dicyclopentadienyl zirconium dichloride, bis [ n-butylcyclopentadienyl ] zirconium dichloride, bis [ methylcyclopentadienyl ] zirconium dichloride, ethylenebridbisindenyl zirconium dichloride, dimethylsilyldiindenyl zirconium dichloride, dimethylsilyldi [ 2-methyl-indenyl ] zirconium dichloride, dimethylsilyldi [ 2-methyl-4-phenyl-indenyl ] zirconium dichloride, dimethylsilyldi [ 2-methyl-4-naphthyl-indenyl ] zirconium dichloride, dimethylsilyldi [ 2-methyl-4-phenyl-indenyl ] zirconium dimethyl, dimethylsilyldi [ 2-methyl-4, 5-benzo-indenyl ] zirconium dichloride, dimethylsilyldi [ fluorenyl ] [ cyclopentadienyl ] zirconium dichloride, benzhydrylfluorenyl ] [ 3-tert-butyl-cyclopentadienyl ] zirconium dichloride and benzhydrylfluorenyl [ cyclopentadienyl ] zirconium dichloride Zirconium dichloride.
According to a preferred embodiment of the present invention, the metallocene compound may be used in solution or suspension with an organic solvent, and the amount of the solvent used is generally 20 to 200 times the weight of the metallocene compound. In general, aromatic hydrocarbons or aliphatic hydrocarbons can be selected as suitable solvents, and specific examples thereof include one or more of toluene, benzene, xylene, pentane, n-hexane, cyclohexane, methylcyclohexane, heptane and isoparaffin thereof.
According to a preferred embodiment of the present invention, the reaction temperature of the solid aluminoxane and the metallocene compound is in the range of from 0 to 150 deg.C, preferably from 40 to 80 deg.C.
According to a preferred embodiment of the present invention, optionally, solid aluminoxane is added to a solvent to form a suspension; mixing solid aluminoxane (or its suspension) with metallocene compound, reacting at 20-50 deg.C for 0.5-5h, cooling, settling, filtering, and washing to obtain solid catalyst.
According to a preferred embodiment of the present invention, the temperature of the vacuum drying process is 0 to 100 ℃.
According to the specific embodiment of the present invention, trimethylaluminum is removed from an organic solvent a solution of aluminoxane in vacuum to obtain aluminoxane solid powder, which is then dissolved in an organic solvent, wherein the solvent can be aromatic hydrocarbon or aliphatic hydrocarbon, such as toluene, benzene, xylene, hexane, heptane, cyclohexane, etc., preferably toluene, and the reaction is carried out at 30 to 110 ℃, preferably 50 to 110 ℃, most preferably 80 to 110 ℃ for 2 to 20 hours, preferably 3 to 15 hours, and then the solid is washed several times with the organic solvent at room temperature, and the organic solvent B is added to precipitate the solid, thereby obtaining a solid aluminoxane suspension. The solid aluminoxane suspension can be directly used for mixing with a metallocene compound, and after reacting for a certain time, a suspension containing a solid catalyst is obtained; or drying to obtain solid aluminoxane. The suspension containing the solid catalyst can be used directly for olefin polymerization; the solid catalyst can also be separated for use in olefin polymerization.
According to a preferred embodiment of the present invention, the metallocene compound and the solid aluminoxane may be reacted first to prepare a catalyst, and then used for olefin polymerization; it is also possible to mix the metallocene compound directly with the solid aluminoxane and the olefinic starting material, to prepare the catalyst simultaneously and to catalyze the olefin polymerization.
According to another aspect of the present invention, there is provided a use of the above catalyst for olefin polymerization, comprising polymerizing the olefin in the presence of the above solid metallocene catalyst.
The olefin polymerization reaction comprises copolymerization reaction and homopolymerization reaction; the copolymerization reaction comprises copolymerization reaction of ethylene and other alpha-olefin; the alpha-olefins include one or more of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene. The homopolymerization reaction comprises ethylene homopolymerization reaction.
In one embodiment of the present invention, the polymerization process comprises a slurry polymerization process and a gas phase polymerization process.
According to the slurry polymerization method, aluminum alkyl is added to a reaction medium to remove impurities during polymerization, then a slurry containing a solid metallocene catalyst or a solid metallocene catalyst is added, the temperature is raised, and then ethylene or ethylene and alpha-olefin are added to carry out polymerization reaction. The polymerization temperature is from 0 ℃ to 150 ℃, preferably from 0 ℃ to 90 ℃. The polymerization pressure is 0.1 to 10.0MPa, preferably 0.1 to 2.0 MPa. The reaction medium is a non-polar medium, such as: c3～C10The saturated alkanes of (1) include alkanes and cycloalkanes, preferably n-hexane.
According to the gas phase polymerization process, it is a gas phase polymerization reaction carried out in a gas phase fluidized bed reactor, which is well known to those skilled in the art. The catalyst is added into a reactor through a feeder, inert gas is used as a diluent in the reactor, and the reactor contains a flowing medium which takes reaction monomers as the flowing medium, wherein the inert gas is nitrogen. The polymerization reaction is carried out at a certain polymerization temperature and pressure. The polymerization pressure is 0.5-3.0 MPa, preferably 1.0-2.5 MPa, and the polymerization reaction temperature is 60-150 ℃, preferably 70-110 ℃.
The invention does not adopt an inert carrier to load the metallocene active component, but leads the aluminoxane to be solidified, and then loads the metallocene active component, compared with the traditional load type metallocene catalyst, the catalyst of the invention has more uniform active center, higher load capacity and better performance. When the catalyst is used in propylene polymerization reaction, the performance is good, and the polymerization activity is obviously improved.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1
To a 250ml glass bottle purged with nitrogen, 200ml of MAO in 10% toluene was added, and the system was warmed to 50 deg.C, stirred, and dried under vacuum to obtain 15.4g of MAO powder as a white support.
Adding 4g of the MAO powder prepared above into a 250ml glass bottle replaced by nitrogen, adding 20ml of toluene for dissolving, starting stirring, heating to 100 ℃, reacting for 10 hours, cooling to room temperature, dropwise adding 10ml of n-hexane, settling, filtering, reacting for 30min with 30ml of n-hexane under stirring, filtering, washing for 3 times with 30ml of n-hexane, filtering, adding 36g of n-hexane to obtain a suspension of solid MAO with the concentration of 10%. Wherein the Al content of the solid MAO was 40.2 wt.%.
Slurry polymerization
After ethylene was replaced several times with nitrogen in a 2-liter stainless autoclave, 1 liter of hexane, 1.0g of the above solid MAO suspension, 1.26mg of bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, m (Al: Zr) ═ 500, was added, ethylene was introduced, and the reaction was carried out at 80 ℃ under 0.7MPa for 1 hour. 30g of random polymer powder with an activity of 1.1 x 10 was obtained7g/molZr.h。
Example 2
To a suspension of 4g of solid MAO prepared in example 1, 126mg of bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride and m (Al: Zr) ═ 200 were added, and the mixture was heated to 40 ℃ to react for 0.5 hour, cooled to room temperature, settled, filtered, washed 3 times with 30ml of n-hexane, filtered, and dried to obtain 4g of a solid catalyst. Weight% of Al in the solid catalyst is 40.1, weight% of Zr: 0.67.
slurry polymerization
After ethylene was replaced several times by nitrogen purging in a 2-liter stainless steel autoclave, 1 liter of hexane, 2 mmol of triethylaluminum, 30mg of the above solid catalyst were added, ethylene was introduced, and the reaction was carried out at 0.7MPa and 80 ℃ for 1 hour. 192g of polymer powder are obtained with an activity of 6400g/gcat.h, corresponding to 8.7X 107g/mol Zr. h, bulk density 0.28g/cm3。
Example 3
To a suspension of 4g of solid MAO prepared in example 1 was added 132mg of bis (1-indenyl) zirconium dichloride, m (Al: Zr) ═ 200, and the mixture was heated to 40 ℃ to react for 0.5 hour, cooled to room temperature, settled, filtered, washed 3 times with 30ml of n-hexane, filtered and dried to obtain 4g of a solid catalyst. Weight% of Al in the solid catalyst is 40.1, weight% of Zr: 0.67.
slurry polymerization
After ethylene was replaced several times by nitrogen purging in a 2-liter stainless steel autoclave, 1 liter of hexane, 2 mmol of triethylaluminum, 25mg of the above solid catalyst were added, ethylene was introduced, and the reaction was carried out at 0.7MPa and 80 ℃ for 1 hour. 205g of polymer powder are obtained with an activity of 8200g/gcat.h, corresponding to 1.1 x 108g/mol Zr. h, bulk density 0.34g/cm3。
Example 4
The same as example 3 except that the compound was rac-ethylenebis (1-indenyl) zirconium dichloride, the data are shown in Table 1.
Examples 5 to 7
The same as example 2 except that m (Al: Zr) was 100, 300 and 500, respectively, and the supported amounts of Zr of the obtained catalysts were 1.2, 0.45 and 0.27, respectively, and the data are shown in Table 1.
Comparative example 1
Solid MAO was directly replaced with 1.8ml of MAO in 10% toluene in a 2 liter stainless steel autoclave, purged with nitrogen, and after several replacements of ethylene, 1 liter of hexane, 1.22mg of bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, m (Al: Zr) ═ 1000, was added, ethylene was introduced, and the reaction was carried out at 0.7MPa, 80 ℃ for 1 hour. 25g of polymer powder, wall-adhering, activity 1.0X 107g/mol Zr. h were obtained.
Comparative example 2
Supports for the cocatalyst
In a 250ml vessel purged with nitrogen, 20 g of the activated silica gel carrier was added, 30ml of toluene was added, the system was warmed to 50 ℃, and a toluene solution of MAO (11g of MAO) was added dropwise, reacted for 4 hours, filtered, washed 3 times with 30ml of toluene, then washed 2 times with hexane, and then dried to obtain a white carrier having excellent fluidity.
Preparation of supported metallocene catalysts
2g of the supported cocatalyst prepared above was added to a 250ml glass bottle substituted with nitrogen, 20ml of toluene was added, stirring was started, 10ml of a toluene solution of bis (1-butyl-3-methylcyclopentadienyl) zirconium chloride, the mass of which was 22.5mg and m (Al: Zr) ═ 200, was added dropwise at room temperature, and the reaction was carried out for 30min under stirring, filtration, washing with 30ml of hexane, filtration, and drying to obtain a pale yellow powder, i.e., a catalyst, having excellent fluidity. Al wt%: 11, Zr wt%: 0.4.
slurry polymerization
After ethylene was replaced several times by nitrogen purging in a 2 liter stainless steel autoclave, 1 liter of hexane, 2 mmol of triethylaluminum and 150mg of the above supported metallocene catalyst were added, ethylene was introduced, and the reaction was carried out at 1.0MPa and 80 ℃ for a certain period of time. And cooling, filtering and drying to obtain the polymer powder.
TABLE 1 polymerization result data for each example and comparative example
As can be seen from the table, the catalyst provided by the invention has good activity and higher bulk density through MAO solidification, and compared with a catalyst using a carrier, the solid catalyst has greatly improved catalytic activity and better application prospect.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A solid metallocene catalyst which is the reaction product of a solid aluminoxane and a metallocene compound.
2. The catalyst according to claim 1, wherein the molar ratio of the solid aluminoxane to the metallocene compound is (10-2000): 1, preferably (20-500): 1.
3. the catalyst according to claim 1 or 2, wherein the solid aluminoxane is prepared by the following method:
removing trimethylaluminum in the aluminoxane to obtain aluminoxane powder;
and (3) carrying out molding treatment on the aluminoxane powder in an organic solvent to obtain solid aluminoxane.
4. A catalyst according to any one of claims 1 to 3, characterised in that the solid aluminoxane has a particle size of 5 to 50 μm, preferably 5 to 30 μm.
5. The catalyst of any one of claims 1 to 4, wherein the aluminoxane comprises a compound of the general formula:
or
In the formulae I and II, R1-R4Are identical or different from each other and are selected from C1-C12Preferably methyl; a is an integer of 4 to 30, preferably an integer of 10 to 30;
the aluminoxane is preferably an alkylaluminoxane, more preferably Methylaluminoxane (MAO) and/or modified methylaluminoxane.
6. The catalyst according to any of claims 1 to 5, wherein the metallocene compound has the general structural formula Cp' X Cp "MQ2(ii) a Wherein Cp 'and Cp' which may be the same or different, are cyclopentadienylene derivative groups, preferably selected from the group consisting of substituted or unsubstituted cyclopentadienyl groups, substituted or unsubstituted indenyl groups and substituted or unsubstituted fluorenyl groups, more preferably substituted or unsubstituted indenyl groups;
when said Cp 'and Cp' comprise substituents, said substituents are selected from C1-C12Is preferably selected from C1-C12One or more of alkyl groups of (a), more preferably one or more selected from methyl, ethyl, propyl, isopropyl, butyl and isobutyl;
x is selected from C1-C4Preferably an ethylene bridge;
said M is selected from group IVB elements, preferably Zr and/or Ti, most preferably Zr;
q is selected from halogen, preferably chlorine.
7. The catalyst according to any one of claims 1 to 6, wherein the reaction temperature of the solid aluminoxane and the metallocene compound is in the range of from 0 to 150 ℃.
8. The catalyst according to any one of claims 1 to 7, wherein the aluminoxane is dissolved in an organic solvent, and the resulting solution is subjected to a vacuum drying treatment to remove trimethylaluminum therefrom, thereby obtaining an aluminoxane powder.
9. The catalyst according to any one of claims 1 to 8, wherein the aluminoxane powder is dissolved in a solvent A, reacted at a certain temperature for a certain period of time, then added with a solvent B to precipitate a solid, and washed and dried to obtain the solid aluminoxane.
10. Use of the solid metallocene catalyst of any one of claims 1 to 9 in olefin polymerization, comprising polymerizing an olefin in the presence of the solid metallocene catalyst of any one of claims 1 to 9.
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| CN1140718A (en) * | 1995-07-14 | 1997-01-22 | 中国石油化工总公司 | Prepn of carried type metallocene compound/aluminoxyane catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1140718A (en) * | 1995-07-14 | 1997-01-22 | 中国石油化工总公司 | Prepn of carried type metallocene compound/aluminoxyane catalyst |
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