CN1789290A - Highly active supporting method of non-metallocene catalyst - Google Patents

Abstract

Highly active loading method for non-metallocene catalysts: the carrier is reacted with a chemical activator to obtain a modified carrier; the magnesium compound is dissolved in a tetrahydrofuran-alcohol mixed system to form a solution, and then the modified carrier is added to the solution for reaction. The composite carrier is obtained after filtering, washing, drying and drying; dissolving the non-metallocene olefin polymerization catalyst in a solvent, reacting with the composite carrier, washing, filtering, drying and drying to obtain a loaded non-metallocene catalyst. It can also be: heat activation treatment is carried out before the carrier reacts with the chemical activator; the composite carrier reacts with the chemical treatment agent before reacting with the catalyst to obtain a modified composite carrier, and the modified composite carrier reacts with the catalyst to obtain a loaded non-metallocene catalyst. The invention can obtain a high-activity supported catalyst; use less methyl aluminoxane to obtain a high-performance supported catalyst; and the polyolefin prepared by using the catalyst prepared by the invention has excellent particle shape.

Description

A highly active loading method for non-metallocene catalysts

technical field

The invention belongs to the technical field of catalyst loading, and relates to a loading method of a non-metallocene catalyst, which is a non-metallocene olefin polymerization catalyst loaded on a composite carrier, and a highly active loaded non-metallocene catalyst is obtained by loading . The composite carrier-supported non-metallocene catalyst can be used for catalyzing olefin polymerization and copolymerization, especially for catalyzing the homopolymerization of ethylene or the copolymerization of ethylene and other α-olefins.

Background technique

Homogeneous transition metal catalysts known to be highly active in olefin polymerization, such as unsupported Ziegler-Natta catalysts, metallocene olefin polymerization catalysts, constrained geometry olefin polymerization catalysts or non-metallocene olefin polymerization catalyst. The coordination atoms of non-metallocene olefin polymerization catalysts are oxygen, nitrogen, sulfur and carbon, etc., and do not contain cyclopentadiene groups. It was discovered and studied in the early 1990s, and its catalytic activity can reach or even exceed Metallocene olefin polymerization catalysts, and at the same time maintain the advantages of metallocene catalyst systems, such as controllable polymers, narrow molecular weight distribution, molecular tailoring of polymers, and controllable molecular weight and branching degree of polymers. Oxygen is weak, and the copolymerization of polar monomers and olefins can be realized, thereby producing functionalized polyolefin materials with excellent performance.

During homogeneous polymerization, the formed polymer will stick to the kettle and entangle the stirring paddle, which has a great impact on the normal operation of the reactor and the heat exchange of materials in the reactor, which is not conducive to industrial continuous production. In addition, a large amount of co-catalyst methylaluminoxane is required in the homogeneous catalytic system, which increases the production cost of polyolefins, and due to the introduction of a large amount of co-catalyst, it also has an adverse effect on product performance. Processing removes the aluminum introduced during polymerization, further adding to the cost of the process. An olefin polymerization and copolymerization catalyst or catalytic system prepared by patent WO03/010207 has a wide range of olefin polymerization and copolymerization properties, and is suitable for various forms of polymerization processes, but requires a high amount of co-catalyst for olefin polymerization. Appropriate olefin polymerization activity is obtained, and there is a phenomenon of sticking in the polymerization process.

According to the experience of industrial application of metallocene olefin polymerization catalysts (Chem Rev, 2000, 100: 1347; Chem Rev, 2000, 100: 1377), the support of homogeneous non-metallocene olefin polymerization catalysts is very necessary.

The main purpose of catalyst support is to improve the polymerization performance of the catalyst and the granulation morphology of the polymer. It is shown that the initial activity of the catalyst is appropriately reduced to a certain extent, thereby reducing or even avoiding the phenomenon of agglomeration or sudden aggregation during the polymerization process; after the catalyst is loaded, it can improve the morphology of the polymer and increase the apparent density of the polymer , can make it meet more polymerization processes, such as gas phase polymerization or slurry polymerization, etc. At the same time, the loading process can greatly reduce the cost of catalyst preparation and olefin polymerization, improve polymerization performance, and extend catalyst polymerization activity life. EP0206794's use of MAO-modified oxide supports and subsequent use of metallocenes objectively limits the ability of the properties of the support material to control the particle size of the polymer. EP685494 uses methylaluminoxane to act on hydrophilic oxides, uses a multifunctional organic crosslinking agent and then uses an activated MAO/metallocene complex, which may reduce the bulk density of the polymer product, which is not conducive to industrial use.

Patent CN1352654 uses organoaluminum, organosilicon, organomagnesium and organoboron compounds to treat the carrier, and then supports heteroatom ligands as a single-center olefin polymerization catalyst. The obtained supported catalyst has high activity and long storage period. EP295312 describes contacting a solution of aluminoxane in the presence of an organic or inorganic particulate support with a solvent in which the aluminoxane is insoluble, resulting in the precipitation of the aluminoxane on the support. WO97/26285 describes a method for preparing a supported metallocene catalyst under high pressure, which has a long production cycle and low loading efficiency. However, in CN1307065, under the action of ultrasonic vibration, the metallocene catalyst is loaded after the carrier is treated with alkyl aluminoxane, and the loading process is not economical.

In order to improve the bonding strength between the carrier and the catalyst, CN1162601 uses a bifunctional crosslinking agent to continue to treat the carrier treated with aluminoxane or alkylaluminum compound. Patent CN1174849 treats the dehydroxylated silica with MAO in toluene medium, and then supports the metallocene catalyst. The article does not give the polymerization activity data of the supported catalyst. Patent CN1120550 proposes a catalyst loading method, which is mainly to heat-activate a hydrophilic, macroporous, and finely divided inorganic carrier first, then react with aluminoxane, then react with a multifunctional organic crosslinking agent, and finally react with The reaction products of the metallocene and the activator are mixed to prepare a supported metallocene catalyst, but the amount of aluminoxane used in the loading process is relatively high. CN1053673 uses microwave action to make the catalyst and the co-catalyst supported on the carrier material contact each other in the suspension, and then prepare a supported catalyst with a stable structure, but this method requires a microwave device and is not easy to operate. CN1323319 adopts catalyst material to impregnate the porous particle carrier of mechanical flow state, is about to spray the catalyst solution equivalent to the pore volume of the carrier onto the carrier, and then dry to obtain the supported catalyst. This loading method objectively requires the solubility of the catalyst to be large enough, otherwise Catalyst loading uniformity and loading cannot be guaranteed. Patent WO96/00243 describes a method for the preparation of a supported catalyst composition, comprising mixing a bridged bis-indenyl metallocene and aluminoxane in a solvent to form a solution, and then combining the solution with a porous support, wherein the The total volume of the solution is less than the volume of the solution when the slurry is formed.

Catalysts supported on anhydrous magnesium chloride show high catalytic activity in olefin polymerization, but such catalysts are very brittle and easily broken in the polymerization reactor, resulting in poor polymer morphology. Silica-supported catalysts have good fluidity and can be used in gas-phase fluidized-bed polymerization, but silica-supported metallocene and non-metallocene catalysts show low catalytic activity. Therefore, if magnesium chloride and silicon dioxide are well organically combined, it is possible to prepare a catalyst with high catalytic activity, controllable particle size and good wear resistance.

EP0878484 reported that the catalyst prepared by MgCl ₂ /SiO ₂ dual carrier supporting zirconium metallocene with low magnesium chloride content (less than 3%) can be used for homopolymerization or copolymerization of ethylene, and has good catalytic activity.

Patent CN1364817 discloses the preparation method and polymerization application of magnesium chloride/silica-supported β-diketone semi-titanium metal catalyst, and its ethylene polymerization activity reaches 7.42×10 ⁶ g polyethylene/mole titanium·hour, but there is no information about Specific data on polymer pelletizing properties.

Patent EP260130 proposes to load a supported metallocene or non-transition metal catalyst on a silica gel carrier treated with methylaluminoxane, where the non-transition metal refers only to ZrCl ₄ , TiCl ₄ or VOCl ₃ , which the patent considers to be optimal What is more is the mixture of organomagnesium or magnesium compound and alkylaluminum on the surface of the carrier, but this process is more complicated and needs to go through many preparation steps.

Patents WO03/047752A1 and WO03/047751A1 provide a method for loading composite catalysts (Ziegler-Natta and metallocene catalysts, or non-metallocene catalysts and metallocene catalysts) on silica gel. According to the patent, the chloride of titanium or vanadium Compounds or oxychlorides are non-metallocene catalyst components and the resulting catalysts are bimetallic catalysts.

The activity of olefin polymerization catalyst is the first condition for its application. However, when the non-metallocene catalyst is supported by an inert carrier, the catalytic olefin polymerization activity will be more or less reduced, and some even reduce the activity by more than an order of magnitude, which leads to the uneconomical application of the supported catalyst. What's more, after the activity is reduced, the ash content of the obtained polymer increases, and an additional deashing process is required in production, which leads to increased cost and complexity of production equipment, which limits its further application in the catalytic production of polyolefins.

Contents of the invention

For this reason, the object of the present invention is to provide a kind of highly active loading method of non-metallocene catalyst on the basis of prior art. Through different polymerization conditions, polyethylene products or copolymerization products of ethylene and other α-olefins can be obtained with different polymerization activities and different properties. The novel catalyst provided by the invention can also improve the morphology of the polymer; increase the packing density of the polymer and improve the polymerization activity.

The invention relates to a loading process of a non-metallocene olefin polymerization catalyst on a composite carrier. It can be used to catalyze olefin polymerization and copolymerization processes, such as catalyzing the homopolymerization of ethylene and the copolymerization of ethylene with other α-olefins, including α-olefins with 3 or more carbon atoms, such as propylene, isobutylene, butene, Pentene, hexene, octene and decene, diolefins such as butadiene, 1,7-octadiene, 1,4-hexadiene or cycloolefins such as norbornene, binary, ternary or higher Multivariate copolymerization.

The highly active loading method of the non-metallocene catalyst of the present invention comprises the following steps:

The carrier is reacted with a chemical activator to obtain a modified carrier;

Dissolving the magnesium compound in the tetrahydrofuran-alcohol mixed system to form a solution, then adding the modified carrier to the solution for reaction, filtering, washing, drying and draining to obtain a composite carrier;

The non-metallocene olefin polymerization catalyst is dissolved in a solvent, then reacted with a composite support, washed, filtered, dried and sucked dry to prepare a supported non-metallocene catalyst.

The optimization scheme of the above method is to add one or two of the following steps:

Thermally activated porous solid as carrier;

The composite carrier reacts with the chemical treatment agent to prepare the modified composite carrier.

The significance of the two steps added to the optimization scheme is explained as follows:

The surface of metal oxides generally has acidic surface hydroxyl groups, which can react with catalysts to deactivate them. Before use, the carrier undergoes a dehydroxylation process, which can be activated by calcination under vacuum or an inert atmosphere. The carrier is calcined at 100-1000° C. for 1-24 hours under inert atmosphere or reduced pressure. The inert atmosphere mentioned here means that the gas only contains a very small amount or does not contain components that can react with the carrier. The calcination conditions are preferably 500-800° C. under N ₂ or Ar atmosphere for 2-12 hours, most preferably 4-8 hours. Heat-activated supports need to be stored under an inert atmosphere.

The purpose of the thermal activation of the silica gel carrier is to make the surface of the carrier have highly active groups. It has been reported (JAm Chem Soc, 1996, 118: 401) that when the drying temperature is 200 ° C to 500 ° C, the easily removed hydroxyl groups is reversibly removed, resulting in low-reactivity siloxane groups, but at drying temperatures above 600 °C, the hydroxyl groups are forcibly removed, converted to water, resulting in high ring stress and very reactive reactive siloxane groups. Chemical activators can also be used to convert functional groups on the surface of the support to other non-reactive siloxane groups.

The composite support can be directly contacted with the solution of the non-metallocene olefin polymerization catalyst, so as to be supported to obtain a supported non-metallocene olefin polymerization catalyst. However, this study found that if a supported non-metallocene olefin polymerization catalyst with better activity is to be obtained, further processing to prepare a modified composite support is very critical. The cost of this treatment step is insignificant compared to the additional activity gained with supported catalysts.

In this process, the composite carrier is contacted with the chemical treatment agent, and the carrier is dipped in the chemical treatment agent solution and stirred for 0.5-72 hours, preferably 2-24 hours, most preferably 2-6 hours, by means of a solution dipping method. The chemical treatment agent is selected from one or more chemical activators selected from aluminoxane, aluminum alkyl, borane, halide, alkyl compound, alkoxy compound or haloalkyl compound of IVA, IVB or VB metal A multi-component treatment agent composed of two kinds.

After adding the steps of the optimization scheme, each step of the method can be described as:

Thermally activated porous solid as carrier;

The heat-activated carrier is reacted with a chemical activator to obtain a modified carrier;

Dissolving the magnesium compound in the tetrahydrofuran-alcohol mixed system to form a solution, then adding the modified carrier to the solution for reaction, filtering, washing, drying and draining to obtain a composite carrier;

The composite carrier is reacted with a chemical treatment agent to prepare a modified composite carrier;

Dissolve the non-metallocene olefin polymerization catalyst in the solvent, and then combine with composite support or modified composite support

After the reaction, it is washed, filtered, dried and sucked dry to obtain a supported non-metallocene catalyst.

The porous solid used in the present invention may be any porous solid having functional groups on the surface. It can be: Copolymers of organic materials containing organofunctional groups such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and the monomers on which the above polymers are based, polyesters, polyamides, polyvinyl chloride , polyacrylate, polymethacrylate, polystyrene, or partially crosslinked polymers, organic functional groups selected from hydroxyl, primary amino, secondary amino, sulfonic acid, carboxyl, amido, N-monosubstituted amides group, sulfonamide group, N-monosubstituted sulfonamide group, mercapto group, imido group and hydrazide group. Preferably partially cross-linked styrene polymers with surface hydroxyl functionality; solid inorganic oxides or halides including group IIA, IIIA, IVA and IVB metal oxides such as silica (silica gel), alumina, magnesia, Titanium oxide, zirconium oxide, thorium oxide, magnesium chloride, and mixtures and mixed oxides composed of inorganic oxides, the functional groups are selected from surface hydroxyl or carboxyl groups. Or oxidized materials prepared by pyrohydrolysis process from gaseous metal oxides or silicon compounds; clays, or molecular sieves, such as mica, montmorillonite, bentonite, diatomaceous earth, ZSM-5, MCM-41. It is more suitable as the carrier of the present invention to have hydroxyl groups on the surface, including silicon oxide, and mixed oxides with one or more IIA and IIIA groups, such as silicon oxide-magnesia mixed oxide, silicon oxide-alumina Mixed oxides, preferably the mixed oxides of silicon oxide, aluminum oxide and silicon oxide and one or more metal oxides of IIA, IIIA groups as carrier material, preferably silica gel as carrier (suitable silica gel carrier is any available through the purchase Commercial products such as Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245, ES70, ES70X, ES70Y, ES757, Aerosil812, or CS-2133 and MS-3040), Silica gel is preferably dried or calcined for 1 to 24 hours at 100-1000°C in an inert atmosphere or under reduced pressure for overheating activation before being used as a carrier;

The surface area (measured by BET method) of the carrier suitable for the present invention is preferably from 10 to 1000 m ² /g, more preferably from 100 to 600 m ² /g. The pore volume of the carrier (measured by nitrogen adsorption method) is preferably 0.1-4 cm ³ /g, more preferably 0.2-2 cm ³ /g. The average particle size of the carrier (measured by laser particle size analyzer) is preferably from 1 to 500 μm, more preferably from 1 to 100 μm. Among the above-mentioned support materials, solid inorganic oxide or halide supports having surface hydroxyl groups inside metal oxides of groups IIA, IIIA, IVA and IVB are preferred, and silica gel is most preferred. It can be in any shape, such as granular, spherical, aggregated or other forms. The hydroxyl content can be determined by known techniques such as infrared spectroscopy, nuclear magnetic resonance, titanium tetrachloride, metal alkyl or metal hydride titration techniques.

The chemical activator used for chemical activation is a compound capable of reacting with hydroxyl groups on the surface of the support, such as metal halides, metal alkyls, metal alkoxides, organosilicon compounds or their mixtures.

The magnesium compound in the loading method is selected from magnesium halide, alkoxymagnesium halide, alkoxymagnesium, or their mixtures. In the process of reacting the thermally activated silica gel with the magnesium compound, the tetrahydrofuran-alcohol mixed solvent is selected from tetrahydrofuran-aliphatic alcohol, tetrahydrofuran-cyclic alcohol or tetrahydrofuran-aromatic alcohol, tetrahydrofuran-ethanol. The magnesium compound is preferably magnesium halide, most preferably magnesium chloride, and the mass ratio of magnesium chloride to silica gel is 1:0.1-40, most preferably 1:1-10.

Dissolve the non-metallocene olefin polymerization catalyst in a solvent, contact with the above-mentioned carrier, and perform solution impregnation or equal volume impregnation process, or first solution impregnation, filter and dry and then perform equal volume impregnation process, so as to complete the non-metallocene catalyst Loading process on the carrier.

The solvent used in the loading process can be mineral oil or different liquid hydrocarbons, typical solvents are hydrocarbon solvents from 5 to 12 carbon atoms, or hydrocarbon solvents substituted by chlorine atoms, or 6 Aliphatic solvents of up to 10 carbon atoms, cycloaliphatic solvents of 6 to 12 carbon atoms, preferably tetrahydrofuran, toluene or hexane.

The non-metallocene olefin polymerization catalyst involved in the present invention is a complex with the following structure:

in:

m: 1, 2 or 3;

q: 0 or 1;

d: 0 or 1;

n: 1, 2, 3 or 4;

M: transition metal atom;

X: Including halogen atoms, hydrogen atoms, C ₁ -C ₃₀ hydrocarbon groups and C ₁ -C ₃₀ substituted hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups Groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups, several Xs can be the same or different, and can also form bonds with each other to form a ring;

The absolute value of the total number of negative charges carried by all ligands in the structural formula should be the same as the absolute value of the positive charge carried by the metal M in the structural formula, and all ligands include X and multidentate ligands;

A: Oxygen atom, sulfur atom, selenium atom, R ²¹ N or R ²¹ P;

B: Refers to nitrogen-containing groups, phosphorus-containing groups or C ₁ -C ₃₀ hydrocarbons;

D: Refers to oxygen atom, sulfur atom, selenium atom, nitrogen-containing group containing C ₁ -C ₃₀ hydrocarbon group, nitrogen-containing group containing C ₁ -C ₃₀ hydrocarbon group or phosphorus-containing group of C ₁ -C ₃₀ hydrocarbon group, Wherein N, O, S, Se, P are coordination atoms;

E: Refers to nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, and phosphorus-containing groups, where N, O, S, Se, and P are coordination atoms;

G: an inert group, including a C1-C30 hydrocarbon group, a C1-C30 substituted hydrocarbon group or an inert functional group;

→: refers to a single bond or a double bond;

......: Refers to coordination bonds, covalent bonds or ionic bonds;

—: refers to a covalent bond or an ionic bond;

R ¹ , R ² , R ³ , R ²¹ , hydrogen, C ₁ -C ₃₀ hydrocarbon group, halogen atom, C ₁ -C ₃₀ substituted hydrocarbon group or inert functional group, R ¹ , R ² , R ³ , R ²¹ The groups can be the same or different, wherein adjacent groups such as R ¹ , R ² , and R ³ can form bonds with each other to form a ring;

Hydrocarbyl refers to C ₁ -C ₃₀ alkyl group, C ₁ -C ₃₀ cyclic hydrocarbon group, C ₂ -C ₃₀ carbon-carbon double bond group, C ₂ -C ₃₀ carbon-carbon triple bond group group, C ₆ -C ₃₀ aromatic hydrocarbon group, C ₈ -C ₃₀ condensed ring hydrocarbon group or C ₄ -C ₃₀ heterocyclic compound.

Non-metallocene catalysts having the following structures are preferred.

The non-metallocene catalyst supported by the composite carrier of the present invention is used as the main catalyst and one of aluminoxane, aluminum alkyl, Lewis acid or boron fluorine compound as the co-catalyst, which can be used to catalyze C2-C10 olefins, especially ethylene , or organic monomers containing functional groups for slurry polymerization, gas phase polymerization, emulsion polymerization, solution polymerization or copolymerization, optimally used for slurry polymerization.

In the present invention, elements and metals belonging to a certain group mean that the group or group of the periodic table of elements corresponds to the group or group organized by the IUPAC system.

Beneficial effects: by adopting the loading method disclosed in the invention, a high loading capacity of the non-metallocene catalyst can be obtained on the loaded catalyst.

By adopting the loading method of the present invention, a high-activity supported catalyst for catalyzing olefin polymerization can be obtained;

The present invention finds that by adopting the loading method provided by the present invention, only a relatively small amount of methyl aluminoxane can be used to obtain a high-performance supported catalyst;

The present invention finds that the polyolefin prepared by using the supported non-metallocene olefin polymerization catalyst prepared by the present invention has excellent particle morphology.

The novel catalyst provided by the invention also improves the morphology of the polymer; increases the bulk density of the polymer.

Detailed ways

Embodiment 1, the highly active loading method of non-metallocene catalyst, mainly comprises the following steps:

The porous solid of the carrier is silica gel Grace 955, and the silica gel is continuously dried or calcined at 500-800°C under _N2 or Ar atmosphere for 4-8 hours. Heat-activated dehydroxylated silica gel needs to be stored under an inert atmosphere.

The chemical activator adopts titanium tetrachloride; the activated carrier is reacted with titanium tetrachloride, and the modified carrier is obtained after filtering, washing, drying and pumping. The mass ratio of titanium tetrachloride and silica gel is 1: 40;

Magnesium chloride is dissolved in a tetrahydrofuran-ethanol mixed system to form a solution, and then the modified carrier is added into the solution, and fully reacted under the stirring condition of 0-60° C. to form a transparent system. The time is 1 to 48 hours, preferably 4 to 24 hours. The composite carrier was obtained after filtering, washing, drying and suctioning. The water content of magnesium chloride should be less than 1% by mass, the average particle size is 1-100 μm, preferably 20-40 μm; the specific surface area is 5-100 m ² /g, preferably 5-30 m ² /g.

Anhydrous magnesium chloride is added to the tetrahydrofuran-alcohol mixed system and stirred to form a solution. Increasing the stirring temperature helps to shorten the dissolution process, and the temperature ranges from 0 to 60°C, preferably 40 to 50°C.

Using methyl aluminoxane to chemically modify the composite carrier to obtain the modified composite carrier;

A non-metallocene olefin polymerization catalyst having the following structure is dissolved in a solvent:

Then it is contacted with a composite support or a modified composite support, washed, filtered, dried and sucked to form a supported non-metallocene catalyst.

The obtained composite carrier, modified composite carrier and supported non-metallocene catalyst replication carrier form are all dry and flowable solid powders.

The "non-metallocene olefin polymerization catalyst" involved in the present invention is well known to those skilled in the art, so the non-metallocene olefin polymerization catalyst in this example can be replaced by any catalyst of the same type, and the reaction steps are basically the same.

Embodiment 1-1 is basically the same as Embodiment 1, but has the following changes:

Dissolve magnesium fluoride in tetrahydrofuran-methanol mixed system to form a solution.

Embodiment 1-2 is basically the same as Embodiment 1, but has the following changes:

Dissolve magnesium iodide in tetrahydrofuran-propanol mixed system to form a solution.

Embodiment 1-3 is basically the same as Embodiment 1, but has the following changes:

Dissolve magnesium bromide in tetrahydrofuran-butanol mixed system to form a solution.

Embodiment 1-4 is basically the same as Embodiment 1, but has the following changes:

The chemical activator adopts metal halide zirconium tetrachloride; the activated carrier is reacted with zirconium tetrachloride, filtered, washed, dried and sucked dry to obtain the modified carrier. The mass ratio of zirconium chloride to silica gel is 1:40;

Magnesium chloride is dissolved in tetrahydrofuran-pentanol mixed system to form a solution.

Embodiment 1-5 is basically the same as Embodiment 1, but has the following changes:

Magnesium chloride was dissolved in tetrahydrofuran-hexanol mixed system to form a solution.

Embodiment 1-6 is basically the same as Embodiment 1, but has the following changes:

The chemical activator adopts metal halide zirconium bromide; the activated carrier is reacted with zirconium bromide, filtered, washed, dried and sucked dry to obtain the modified carrier. The mass ratio of zirconium bromide to silica gel is 1:40;

Magnesium chloride was dissolved in tetrahydrofuran-hexanol mixed system to form a solution.

Embodiment 1-7 is basically the same as Embodiment 1, but has the following changes:

The chemical activator adopts metal halide aluminum fluoride; the activated carrier is reacted with aluminum fluoride, filtered, washed, dried and drained to obtain the modified carrier. The mass ratio of aluminum fluoride to silica gel is 1:40;

Magnesium chloride was dissolved in a tetrahydrofuran-heptanol mixed system to form a solution.

Embodiment 2 is basically the same as Embodiment 1, but has the following changes:

The non-metallocene olefin polymerization catalyst was changed to a compound of the following structural formula:

The thermal activation conditions of the carrier silica gel are: 100-1000°C, under reduced pressure, dry or roast for 2-12 hours;

The mass ratio of magnesium chloride to silica gel is 1: 0.1;

The chemical activator adopts titanium tetrachloride;

After heat-activated silica gel reacts with titanium tetrachloride solution for a certain period of time, the modified carrier is obtained by filtering, washing and drying. The length of reaction time between silica gel and titanium tetrachloride solution affects the content of titanium tetrachloride on the surface of silica gel. A long-term reaction will result in a silica gel carrier with high titanium tetrachloride content, and the opposite is true for a short time. It is found by the present invention that a better result can be obtained in 0.5-24 hours, and the optimum reaction time is 1-6 hours. The temperature is not limited here, but it is obvious that under lower temperature conditions, the loss of titanium tetrachloride leaving the reaction system due to vaporization is very small, which is conducive to the loading efficiency of titanium tetrachloride on the silica gel carrier. , Increase the content of titanium tetrachloride. For catalytic olefin polymerization catalysts, high titanium tetrachloride content will help to improve the catalytic olefin polymerization activity of the catalyst, but in the actual operation process, it is not easy to increase the content of titanium tetrachloride, and generally requires a long time at low temperature Under certain conditions, use pure titanium tetrachloride to soak the carrier, or use multiple times to soak the carrier. One of the characteristics of the present invention is that it can provide a support with high titanium tetrachloride content under mild conditions. The titanium tetrachloride solution can be any mixture of titanium tetrachloride and solvent that can form stable and uniform properties with titanium tetrachloride, preferably a hexane solution of titanium tetrachloride. Hexane solvent is the best choice for filtering and washing solvent;

The dried modified silica gel support is a dry flowable powder.

The tetrahydrofuran-alcohol mixed system is changed to tetrahydrofuran-cycloalcohol, and this embodiment is tetrahydrofuran-cyclohexanol;

Wherein the dissolved magnesium compound is changed to alkoxymagnesium halide, and the present embodiment is MgClOCH ₃ ;

The modifying agent for chemically modifying the composite carrier is changed to alkylaluminum, for example: trimethylaluminum, triethylaluminum, triisobutylaluminum, etc.

Embodiment 2-1 is basically the same as Embodiment 2, but has the following changes:

Tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclopentanol;

The magnesium compound is changed to MgClOCH ₂ CH ₃ ;

The modifier for chemically modifying the composite support was changed to triethylaluminum.

Embodiment 2-2 is basically the same as Embodiment 2, but has the following changes:

Tetrahydrofuran-alcohol mixed system was changed to tetrahydrofuran-cyclooctyl alcohol;

The magnesium compound is changed to MgClOC ₄ H ₉ ;

The modifier for chemically modifying the composite carrier is changed to triisobutylaluminum;

Embodiment 2-3 is basically the same as Embodiment 2, but has the following changes:

The magnesium compound is changed to MgBrOCH ₃ ;

Embodiment 2-4 is basically the same as Embodiment 2, but has the following changes:

The magnesium compound was changed to MgBrOCH ₂ CH ₃ .

Embodiment 2-5 is basically the same as Embodiment 2, but has the following changes:

The magnesium compound was changed to MgBrOC ₄ H ₉ .

Embodiment 3 is basically the same as Embodiment 1, but has the following changes:

The thermal activation conditions of the carrier silica gel are: drying or roasting under Ar atmosphere for 1 to 24 hours;

The mass ratio of magnesium chloride to silica gel is 1:10;

Embodiment 4 is basically the same as Embodiments 1 to 3, but has the following changes:

Silica gel does not undergo thermal activation, and directly reacts with magnesium chloride to obtain a composite carrier; the mass ratio of magnesium chloride to silica gel is 1:1.

Embodiment 5 is basically the same as Embodiments 1 to 3, but has the following changes:

The composite carrier directly reacts with the non-metallocene olefin polymerization catalyst, does not interact with chemical treatment agents, and does not need to be made into a modified composite carrier.

Embodiment 6 is basically the same as Embodiments 1 to 3, but has the following two changes at the same time:

Silica gel does not undergo thermal activation, and directly reacts with magnesium chloride to obtain a composite carrier; the mass ratio of magnesium chloride to silica gel is 1:1;

The composite carrier directly reacts with the non-metallocene olefin polymerization catalyst, does not interact with chemical treatment agents, and does not need to be made into a modified composite carrier.

Embodiment 7 is basically the same as Embodiments 1 to 3 or 4 to 6, but has the following changes:

The porous solid as the carrier is changed to: solid inorganic oxides or halides including metal oxides of groups IIA, IIIA, IVA and IVB, such as: alumina, magnesia, titania, zirconia, thorium oxide, and magnesium chloride.

Embodiment 8 is basically the same as Embodiments 1 to 3 or 4 to 6, but has the following changes:

The chemical treatment agent used to prepare the modified composite carrier is changed to: a mixture of methyl aluminoxane and titanium tetrachloride;

The tetrahydrofuran-alcohol mixed system is changed to tetrahydrofuran-aromatic alcohol, such as: tetrahydrofuran-phenylmethanol, tetrahydrofuran-phenylethanol, tetrahydrofuran-phenylbutanol, tetrahydrofuran-naphthylmethanol, tetrahydrofuran-naphthyl ethanol, tetrahydrofuran-naphthylbutyl Alcohol, etc.;

The dissolved magnesium compound is changed to: magnesium alkoxide, for example: Mg(OCH ₃ ) ₂ , Mg(OCH ₂ CH ₃ ) ₂ , Mg(OC ₄ H ₉ ) _{2 ,} etc.;

Various chemical activators, magnesium compounds, tetrahydrofuran-alcohol mixed solvents, solvents and other factors involved in the present invention can be replaced by various known equivalents within the professional scope of those skilled in the art without affecting the implementation of the method of the present invention .

Claims (8)

1. A highly active loading method for non-metallocene catalysts, comprising the following steps: The carrier is reacted with a chemical activator to obtain a modified carrier; Dissolving the magnesium compound in the tetrahydrofuran-alcohol mixed system to form a solution, then adding the modified carrier to the solution for reaction, filtering, washing, drying and draining to obtain a composite carrier; The non-metallocene olefin polymerization catalyst is dissolved in a solvent, then reacted with a composite support, washed, filtered, dried and sucked dry to prepare a supported non-metallocene catalyst. 2. According to the method for highly active loading of non-metallocene catalysts according to claim 1, it is characterized in that one or both of the following steps are also provided: The porous solid as the carrier is subjected to thermal activation treatment before reacting with the chemical activator; Before the composite support reacts with the non-metallocene olefin polymerization catalyst, it reacts with a chemical treatment agent to obtain a modified composite support, and the modified composite support reacts with the non-metallocene olefin polymerization catalyst to obtain a loaded non-metallocene catalyst. 3. The highly active loading method of the non-metallocene catalyst according to claim 1 or 2, characterized in that: The porous solid as the carrier is a porous organic material: inorganic oxides including metal oxides of groups IIA, IIIA, IVA and IVB, or oxide mixtures and mixed oxides, or gaseous metal oxides or silicon compounds through high temperature Oxidized materials produced by hydrolysis processes; The chemical activator is a compound capable of reacting with hydroxyl groups on the surface of the carrier, selected from metal halides, metal alkyls, metal alkoxides, organosilicon compounds or mixtures thereof; The magnesium compound is selected from magnesium halides, alkoxy magnesium halides, alkoxy magnesium, or mixtures thereof; In the process of reacting the carrier with the magnesium compound, the tetrahydrofuran-alcohol mixed solvent is selected from tetrahydrofuran-aliphatic alcohol, tetrahydrofuran-cyclic alcohol or tetrahydrofuran-aromatic alcohol; The solvent used in the loading process is mineral oil or different liquid hydrocarbons, selected from hydrocarbon solvents from 5 to 12 carbon atoms, or hydrocarbon solvents substituted by chlorine atoms, or from 6 to 10 carbon atoms Aliphatic solvents, or cycloaliphatic solvents of 6 to 12 carbon atoms. 4. The highly active loading method of non-metallocene catalyst according to claim 3, characterized in that: The non-metallocene olefin polymerization catalyst is a complex with the following structure: in: m: 1, 2 or 3; q: 0 or 1; d: 0 or 1; n: 1, 2, 3 or 4; M: transition metal atom; X: Including halogen atoms, hydrogen atoms, C ₁ -C ₃₀ hydrocarbon groups and C ₁ -C ₃₀ substituted hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups Groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups, several Xs can be the same or different, and can also form bonds with each other to form a ring; The absolute value of the total number of negative charges carried by all ligands in the structural formula should be the same as the absolute value of the positive charge carried by the metal M in the structural formula, and all ligands include X and multidentate ligands; A: Oxygen atom, sulfur atom, selenium atom, R ²¹ N or R ²¹ P; B: Refers to nitrogen-containing groups, phosphorus-containing groups or C ₁ -C ₃₀ hydrocarbons; D: Refers to oxygen atom, sulfur atom, selenium atom, nitrogen-containing group containing C ₁ -C ₃₀ hydrocarbon group, nitrogen-containing group containing C ₁ -C ₃₀ hydrocarbon group or phosphorus-containing group of C ₁ -C ₃₀ hydrocarbon group, Wherein N, O, S, Se, P are coordination atoms; E: Refers to nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, and phosphorus-containing groups, where N, O, S, Se, and P are coordination atoms; G: an inert group, including a C1-C30 hydrocarbon group, a C1-C30 substituted hydrocarbon group or an inert functional group; →: refers to a single bond or a double bond; ......: Refers to coordination bonds, covalent bonds or ionic bonds; -: Refers to a covalent bond or an ionic bond; R ¹ , R ² , R ³ , R ²¹ , hydrogen, C ₁ -C ₃₀ hydrocarbon group, halogen atom, C ₁ -C ₃₀ substituted hydrocarbon group or inert functional group, R ¹ , R ² , R ³ , R ²¹ The groups can be the same or different, wherein adjacent groups such as R ¹ , R ² , and R ³ can form bonds with each other to form a ring; Hydrocarbyl refers to C ₁ -C ₃₀ alkyl group, C ₁ -C ₃₀ cyclic hydrocarbon group, C ₂ -C ₃₀ carbon-carbon double bond group, C ₂ -C ₃₀ carbon-carbon triple bond group group, C ₆ -C ₃₀ aromatic hydrocarbon group, C ₈ -C ₃₀ condensed ring hydrocarbon group or C ₄ -C ₃₀ heterocyclic compound. 5. The highly active loading method of non-metallocene catalyst according to claim 4, characterized in that: Described non-metallocene olefin polymerization catalyst is selected from non-metallocene catalysts having the following structure:

The porous solid as the carrier adopts silica gel; The magnesium compound is magnesium chloride, and the mass ratio of magnesium chloride to silica gel is 1:0.1-40; The tetrahydrofuran-alcohol mixed solvent adopts tetrahydrofuran-ethanol; The solvent mineral oil or different liquid hydrocarbons adopt tetrahydrofuran, toluene or hexane. 6. The high activity loading method of non-metallocene catalyst according to claim 4 or 5, characterized in that: The silica gel used as a carrier is activated by overheating before being used as a carrier, and the condition is: dry or calcinate for 1-24 hours at 100-1000°C, in an inert atmosphere or under reduced pressure; The mass ratio of described magnesium chloride and silica gel is 1: 1; The mass ratio of magnesium chloride to tetrahydrofuran is 1:5-25, and the mass ratio of magnesium chloride to ethanol is 1:1-8. 7. The high activity loading method of non-metallocene catalyst according to claim 6, characterized in that: The conditions for overheating activation of silica gel as a carrier are: at 500-800° C., N ₂ or Ar atmosphere for 2-12 hours; the mass ratio of magnesium chloride to tetrahydrofuran is 1: 10-20, and the mass ratio of magnesium chloride to ethanol is 1: 2 ~ 6. 8. The method for highly active loading of non-metallocene catalysts according to claim 7, characterized in that: The time for the silica gel as a carrier to be thermally activated is 4 to 8 hours.