CN1281634C - Loaded method of Non-metallocene catalyst loaded by composite carrier and polymerizing application - Google Patents

Abstract

A carrying method of a non-metallocene catalyst carried by a composite carrier and a polymerization application relate to a preparation method of a non-metallocene olefin polymerization catalyst carried by a composite carrier, and an application of the catalyst in the polymerization process and the copolymerization process of olefin; especially, the catalyst is used for the homopolymerization of ethylene or the copolymerization of ethylene and other alpha-olefin. The method comprises: after being thermally activated, silica gel reacts with the tetrahydrofuran-ethanol solution of magnesium chloride to prepare the composite carrier; then, the composite carrier reacts with a chemical treating agent to prepare a modified composite catalyst; finally, the non-metallocene olefin polymerisation catalyst is carried by a solution method or an equivolume immersion method. The carried non-metallocene catalyst prepared by the carrying process is dry fluxible solid powder and can be used for the slurry or gas phase homopolymerization or copolymerization of C2 to C10 olefin or phenylethylene, especially ethylene, or organic monomers comprising functional groups. Copolymerization products with a high melting point and a good particle shape can be obtained under the condition of low aluminoxane consumption.

Description

Supporting method and polymerization application of non-metallocene catalyst supported by composite carrier

Technical field

The present invention is a preparation method of a non-metallocene olefin polymerization catalyst supported by a composite carrier, and its application in the process of olefin polymerization and copolymerization, especially for the homopolymerization of ethylene or the copolymerization of ethylene and other α-olefins, belonging to Catalyst loading technology and technical field of olefin polymerization.

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. Among them, the Ziegler-Natta catalyst is a multi-active-center olefin polymerization catalyst, and the latter three are single-active-center olefin polymerization catalysts. Metallocene olefin polymerization catalysts and constrained geometry olefin polymerization catalysts all contain cyclopentadienyl ligands in the catalyst structure, while non-metallocene olefin polymerization catalysts have coordination atoms such as oxygen, nitrogen, sulfur, and carbon, etc., and do not contain rings. The pentadiene group was discovered and studied in the early 1990s. Its catalytic activity can reach or even exceed that of metallocene olefin polymerization catalysts, while maintaining the controllable polymer of the metallocene catalyst system, narrow molecular weight distribution, and Polymer molecular tailoring, polymer molecular weight and branching degree can be adjusted, etc., and because this type of catalyst is weak in oxophilicity, it can realize the copolymerization of polar monomers and olefins, 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. EP 0206794's use of MAO-modified oxide supports and subsequent use of metallocenes objectively limits the ability 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. EP 295312 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. CN 1053673 uses microwave action to make the catalyst and the co-catalyst supported on the carrier material contact each other in the suspension, and then make a supported catalyst with a stable structure, but this method requires a microwave device, and the operation is not simple. 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.

The article that K.Soga et al. published in J.Polym.Sci., Polym.Chem.Ed.35, 291～311 discusses the polymerization performance of the catalyst prepared by loading cyclopentadiene titanium trichloride on the magnesium chloride carrier , the catalyst can be used in combination with triisobutylaluminum cocatalyst to prepare polypropylene, and has high polymerization activity.

EP 0878484 reported that a catalyst prepared by MgCl ₂ /SiO ₂ double-supported 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 CN 1364817 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× ¹⁰⁶ g polyethylene/mole titanium·hour, but there is no Specific data on polymer granulation properties.

Contents of invention

Technical problem: The purpose of the present invention is to provide a method for loading non-metallocene olefin polymerization catalysts on the basis of the prior art.

Technical solution: The present invention relates to the loading process of a new type of non-metallocene olefin polymerization catalyst on a composite carrier, and its application in olefin polymerization and copolymerization, especially for the homopolymerization of ethylene and the combination of ethylene and other α - olefins, including copolymerization of alpha-olefins of 3 or more carbon atoms, such as with propylene, isobutene, butene, pentene, hexene, octene and decene, diolefins such as butadiene, 1,7- Copolymerization of octadiene, 1,4-hexadiene or cyclic olefins such as norbornene, etc.

The loading method of the non-metallocene catalyst supported by composite carrier of the present invention comprises the following steps:

1. Dry or calcinate the porous solid as a carrier at 100-1000°C, inert atmosphere or reduced pressure for 1-24 hours for thermal activation;

2. Dissolve the magnesium compound in the tetrahydrofuran-alcohol mixed system to form a solution, then add the heat-activated porous solid into the solution, fully react under stirring conditions at 0-60°C to form a transparent system; filter, wash, dry and The composite carrier is obtained after being drained; or the transparent solution is added to a non-polar organic solvent to precipitate and fully separated, then filtered, washed, dried and drained to obtain a composite carrier; the composite carrier is obtained;

3. Use any one or more chemical reagents that can interact with the surface functional groups of the composite carrier, such as aluminoxane, IIIA, IVB or VB metal halides, alkyl compounds or haloalkyl compounds, methyl aluminoxane or tetra Titanium chloride, or a mixture of the two, is used to chemically modify the composite carrier to obtain a modified composite carrier;

4. The non-metallocene olefin polymerization catalyst is dissolved in a solvent, and then contacted with a composite carrier or a modified composite carrier for 12 to 72 hours, then washed, filtered, dried and pumped to form a loaded non-metallocene catalyst.

Wherein step 3 is an optional step.

Porous solids as supports are: porous organic materials, inorganic oxides including metal oxides of groups IIA, IIIA, IVA and IVB, as well as oxide mixtures and mixed oxides, or gaseous metal oxides or silicon compounds through high temperature Oxidized material prepared by hydrolysis process, or clay, or molecular sieve, silica gel.

The magnesium compound in the loading method is magnesium halide, alkoxymagnesium halide, alkoxymagnesium, or their mixture, or magnesium chloride. In the process of reacting the thermally activated porous solid with the magnesium compound, the tetrahydrofuran-alcohol mixed solvent is tetrahydrofuran-aliphatic alcohol, tetrahydrofuran-cyclic alcohol or tetrahydrofuran-aromatic alcohol, tetrahydrofuran-ethanol. The porous solid is silica gel, the magnesium compound is magnesium halide, and the mass ratio of magnesium halide to silica gel is 1:0.1-40, preferably 1:1-10. The solvent used to dissolve the non-metallocene olefin polymerization catalyst solution in the solvent is mineral oil or different liquid hydrocarbons, typical solvents are hydrocarbon solvents from 5 to 12 carbon atoms, or substituted by chlorine atoms Hydrocarbon solvents, or aliphatic solvents of 6 to 10 carbon atoms, cycloaliphatic solvents of 6 to 12 carbon atoms, or tetrahydrofuran, toluene or hexane.

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;

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

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

-: Refers to covalent bond or 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.

The olefin polymerization process of the non-metallocene catalyst supported by the composite carrier of the present invention uses the non-metallocene catalyst supported by the composite carrier as the main catalyst, and uses one of aluminoxane, alkylaluminum, Lewis acid or borofluorine compound as the co-catalyst, so that Organically polymerizable monomers are slurry polymerized, gas phase polymerized, emulsion polymerized, solution polymerized, or copolymerized under conditions sufficient to effect the reaction. The organic polymer monomer is a C2-C10 olefin, especially ethylene, or an organic monomer containing a functional group.

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 effect: adopting the loading method disclosed in the present invention can obtain a very high content of non-metallocene olefin polymerization catalyst, whose mass ratio can reach one-third of the whole loaded catalyst, and can still obtain olefin polymer with good particle shape.

The present invention finds that the polyethylene prepared by using the supported non-metallocene olefin polymerization catalyst prepared by the present invention has a very high melting point.

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

Description of drawings

Fig. 1 is the particle size distribution (average 409.7 μm) of the sample of the present invention (Example 1).

Fig. 2 is the particle size distribution (average 689.8 μm) of another sample (Example 4) of the present invention.

Fig. 3 is a graph showing the results of melting point measurement of the sample of the present invention (Example 1).

Detailed ways

The loading method of the non-metallocene catalyst supported by composite carrier of the present invention comprises the following steps:

1. Dry or calcinate the porous solid as carrier at 100-1000°C, inert atmosphere or reduced pressure for 1-24 hours for thermal activation;

2. The magnesium compound is dissolved in the tetrahydrofuran-alcohol mixed system to form a solution, and then the heat-activated porous solid is added to the solution, and fully reacted under stirring conditions at 0-60°C to form a transparent system; after filtering, washing, drying and pumping After drying, a composite carrier is obtained; or the transparent solution is added to a non-polar organic solvent to precipitate and fully separate out, then filtered, washed, dried and drained to obtain a composite carrier;

3. Use any one or more chemical reagents that can interact with the surface functional groups of the composite carrier, such as aluminoxane, IIIA, IVB or VB metal halides, alkyl compounds or haloalkyl compounds, methyl aluminoxane or tetra Titanium chloride, or a mixture of the two, is used to chemically modify the composite carrier to obtain a modified composite carrier;

4. The metallocene olefin polymerization catalyst is dissolved in a solvent, and then contacted with a composite carrier or a modified composite carrier for 12 to 72 hours, then washed, filtered, dried and sucked to form a loaded non-metallocene catalyst.

Wherein step (3) is an optional step.

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

The porous solid used in the present invention may be any porous solid having functional groups on the surface. It can be:

a. Copolymers of organic materials containing organic functional groups such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and the monomers on which the above polymers are based, polyester, polyamide, polyvinyl chloride, poly Acrylate, polymethacrylate, polystyrene, or partially crosslinked polymers, organic functional groups selected from hydroxyl, primary amino, secondary amino, sulfonic acid, carboxyl, amido, N-monosubstituted amido, Sulfonamide, N-monosubstituted sulfonamide, mercapto, imido and hydrazide. Preferably partially crosslinked styrene polymers with surface hydroxyl functional groups;

b. Solid inorganic oxides or halides including metal oxides of groups IIA, IIIA, IVA and IVB, such as silicon oxide (silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide, thorium oxide, magnesium chloride, and A mixture of inorganic oxides, the functional group is selected from surface hydroxyl or carboxyl. It is more suitable to have hydroxyl groups on the surface, including silicon oxide and one or more mixed oxides of IIA and IIIA groups, such as silicon oxide-magnesia mixed oxide, silicon oxide-alumina mixed oxide, Preference is given to silicon oxide, aluminum oxide and mixed oxides of silicon oxide and one or more metal oxides of groups IIA, IIIA as support materials, most preferably silica gel.

C. Oxidized materials prepared from gaseous metal oxides or silicon compounds through a pyrohydrolysis process.

d. Clay, or molecular sieve, such as mica, montmorillonite, bentonite, diatomaceous earth, ZSM-5, MCM-41.

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. A suitable silica gel support is any commercial product available through Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245, ES70, ES70X, ES757, Aerosil 812, or CS- 2133 and MS-3040.

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 silica gel carrier is calcined at 100-1000° C. for 1-24 hours in an inert atmosphere or under 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 dehydroxylated silica gel needs to be stored under an inert atmosphere.

The purpose of thermal activation of the silica gel carrier is to make the surface of the carrier have highly active groups. It is reported (J AmChem Soc, 1996, 118: 401) that when the drying temperature is 200 ° C ~ 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 solvent involved in the present invention can be mineral oil and different liquid hydrocarbons. Typical solvents are hydrocarbon solvents from 5 to 12 carbon atoms, or hydrocarbon solvents substituted by chlorine atoms, such as dichloromethane, or ether-based solvents such as diethyl ether or tetrahydrofuran, acetone, ethyl acetate, etc. can also be used . Aromatic solvents such as toluene and xylene are preferred; or aliphatic solvents of 6 to 10 carbon atoms, such as hexane, heptane, octane, nonane, decane and their isomers, 6 to 12 carbon atoms Atomic cycloaliphatic solvents such as hexane; or mixtures thereof. Most preferred are tetrahydrofuran, toluene or hexane.

The thermally activated porous solid needs to be further reacted with magnesium compounds to make a composite support. Magnesium compounds include magnesium halides, such as MgCl ₂ , MgBr ₂ , MgI ₂ ; alkoxy magnesium halides, such as Mg(OMe)Cl, Mg(OEt)Cl, Mg(OPr)Cl, Mg(OBu)Cl; alkoxy Magnesium, such as Mg(OEt) ₂ , Mg(OiPr) ₂ , Mg(OBu) ₂ , and mixtures thereof. Magnesium halides are preferred, and magnesium chloride is most preferred. 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 into the tetrahydrofuran-alcohol mixed solvent 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. The alcohol in the tetrahydrofuran-alcohol mixed solvent mentioned here can be aliphatic alcohol, such as methyl alcohol, ethanol, Virahol, butanol, hexanol, 2-methylpentanol, 2-hexylbutanol, n-heptanol, 2-Ethylhexanol, n-octanol, decyl alcohol, etc., cycloalkanol, such as cyclohexanol, methylcyclohexanol; aromatic alcohol, such as benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, etc., preferably Fatty alcohols, most preferably ethanol.

Then add silica gel into the solution, fully react under the condition of stirring at 0-60°C to form a transparent system. The time is 1 to 48 hours, preferably 4 to 24 hours. The mass ratio of magnesium chloride to silica gel is 1:0.1-40, preferably 1:1-10. The tetrahydrofuran-alcohol mixed solvent described here may be tetrahydrofuran-fatty alcohol or tetrahydrofuran-aromatic alcohol, preferably tetrahydrofuran-ethanol. The mass ratio of magnesium halide to silica gel is 1:0.1-40, preferably 1:1-10. The mass ratio of magnesium chloride to tetrahydrofuran is 1:5-25, preferably 1:10-20. The mass ratio of magnesium chloride to ethanol is 1:1-5, preferably 1:1-3. If the amount of ethanol solvent used is too small, magnesium chloride is not easy to form a homogeneous solution, and if the amount of ethanol solvent used is too large, the economic aspect is unfavorable, and the performance of the prepared catalyst is also unsatisfactory. Filter the above transparent system, wash it with toluene solvent for many times, and then drain it to obtain a composite carrier, or add a non-polar organic solvent, such as hexane, to the system, let the precipitate fully separate out, filter it, and wash it with hexane solvent for many times, Finally, dry and vacuum to obtain a composite carrier.

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.

Specifically, aluminoxane adopts the linear type (I)

That is R-(Al(R)-O) _n -AlR ₂

and/or alumoxanes of the cyclic type alumoxane (II).

That is -(Al(R)-O-) _n+2

In structures (I) and (II), the R groups can be the same or different, and are C1-C8 alkyl groups, including methylalumoxane, ethylalumoxane, isobutylalumoxane, butylaluminum Oxygen, etc. Preferably the R groups are identical and are methyl, isobutyl, phenyl or benzyl, most preferably methyl, and n is an integer of 1-50, preferably 10-30.

Aluminum alkyls or boron alkyls are compounds of the general formula (III):

N(R) ₃

Wherein: N is aluminum or boron, R is the same as defined in structures (I) and (II), and each of the three R groups can be the same or different. Including metal alkyl compounds including trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum , tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, tripentyl aluminum, tri-p-tolyl aluminum, dimethyl Aluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron,

Halides, alkyl compounds, alkoxy compounds or haloalkyl compounds of Group IVA, IVB or VB metals, such as SiCl ₄ , SiBr ₄ , Si(OC ₂ H ₅ ) ₃ Cl, Si(OC ₂ H ₅ )Cl ₃ , S(OC ₄ H ₉ )Cl ₃ , Si(OC ₄ H ₉ ) ₃ Cl, Si(OC ₃ H ₇ ) ₂ Cl _2, etc.; TiCl ₄ , TiBr ₄ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ )Cl ₃ , Ti(OC ₄ H ₉ )Cl ₃ , Ti(OC ₄ H ₉ ) ₃ Cl, Ti(OC ₃ H ₇ ) ₂ Cl ₂ , Ti(OC ₆ H ₁₃ ) ₂ Cl ₂ , Ti(OC ₈ H ₁₇ ) ₂ Br, Ti(OC ₁₂ H ₂₅ )Cl ₃ ; VCl ₄ , VBr ₄ , V(OC ₂ H ₅ ) ₃ Cl, V(OC ₂ H ₅ )Cl ₃ , V(OC ₄ H ₉ )Cl ₃ , V(OC ₄ H ₉ ) ₃ Cl, ZrCl ₄ , ZrBr ₄ , Zr(OC ₂ H ₅ ) ₃ Cl, Zr(OC ₂ H ₅ )Cl ₃ , Zr(OC ₄ H ₉ ) Cl ₃ , Zr(OC ₄ H ₉ ) ₃ Cl, Zr(OC ₃ H ₇ ) ₂ Cl ₂ , Zr(OC ₆ H ₁₃ ) ₂ Cl ₂ , Zr(OC ₈ H ₁₇ ) ₂ Br, Zr(OC ₁₂ H ₂₅ ) Cl ₃ .

The above reagents may be used alone or in combination. Preferred are aluminoxane, halogen compounds of titanium or zirconium, or a mixture containing aluminoxane, more preferably methylalumoxane, or titanium tetrachloride, or a binary chemical treatment agent composed of both.

The present invention unexpectedly finds that directly using titanium halides, such as TiCl ₄ as a chemical treatment agent, compared with using methyl aluminoxane alone or a binary system composed of methyl aluminoxane and TiCl ₄ , can still obtain Very high polymerization activity and active life, and more surprisingly, the particles of the polymer are spherical particles with uniform size.

The chemical treatment agent can be added quickly or slowly, preferably slowly, such as dropwise addition, which is beneficial to the dispersion process.

The washing, filtering, drying and draining process is to adopt methods well known in the art, such as rinsing, that is, under a closed or active atmosphere, on a sand core funnel that cannot pass through the leached solid but can pass through the solvent, the solvent is passed repeatedly. Rinse to achieve the purpose of washing and filtering; or use grate washing, that is, stand to remove the upper liquid, and then add solvent, repeat these processes to achieve the purpose of washing and filtering; or the most common method is to put the system that needs to be washed and filtered into the In the sand core funnel, the solvent is removed by suction filtration, then the solvent is added, and then suction filtration is performed, so as to achieve the purpose of washing and filtration. Rinse washing has the best washing effect, but it is uneconomical and takes a long time. Grinding is simple and easy, but the effect is not thorough. The present invention prefers the suction filtration method. The washing and filtering process needs to be repeated at least three times. The more times of natural washing, the better the washing effect, but it will also increase the consumption of solvent. Preferably 3 to 5 times. The treatment temperature and washing temperature are not strictly limited in this patent, and may be 0°C to 100°C. It is preferably between 20°C and 80°C, and optimally between 40°C and 60°C.

The solid is dried under reduced pressure at a temperature of about 0-120° C. until fluid catalyst carrier powder is obtained. The length of this drying process depends on the temperature used, as well as the ability of the vacuum system and the airtightness of the system.

The non-metallocene olefin polymerization catalyst involved in the present invention is a complex (IV) having the following structure

It mainly includes catalysts IVA and IVB of the following structures.

In order to understand catalyst IVA more clearly, we can use IVA-1, IVA-2, IVA-3 and IVA-4 to refine the description.

In order to understand catalyst IVB more clearly, we can use IVB-1, IVB-2, IVB-3 and IVB-4 to refine the description.

In all structures above:

m: 1, 2 or 3;

q: 0 or 1;

d: 0 or 1;

M: transition metal atoms, especially titanium, zirconium, hafnium, chromium, iron, cobalt, nickel, palladium;

n: 1, 2, 3 or 4;

X: It includes halogen atoms, hydrogen atoms, Cl-C30 hydrocarbon groups and C1-C30 substituted hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, and Phosphorous groups, silicon-containing groups, germanium-containing groups, or tin-containing groups, several Xs in the structural formula can be the same or different, and can also form bonds with each other to form a ring;

The halogen atoms here include fluorine, chlorine, bromine or iodine;

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;

-PR²⁸R²⁹、-P(O)R³⁰R³¹、砜基、亚砜基、-Se(O)R³⁹；A: Oxygen atom, sulfur atom, selenium atom, -NR ²³ R ²⁴ , -N(O)R ²⁵ R ²⁶ ,

-PR ²⁸ R ²⁹ , -P(O)R ³⁰ R ³¹ , sulfone group, sulfoxide group, -Se(O)R ³⁹ ;

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

-N(O)R²⁵R²⁶、 -P(O)R³⁰R³¹、-P(O)R³²(OR³³)、其中N、O、S、Se、P为配位原子；D: Refers to oxygen atom, sulfur atom, selenium atom, nitrogen-containing group containing C ₁ -C ₃₀ hydrocarbon group, phosphorus-containing group containing C ₁ -C ₃₀ hydrocarbon group, sulfone group, sulfoxide group,

-N(O)R ²⁵ R ²⁶ , -P(O)R ³⁰ R ³¹ , -P(O)R ³² (OR ³³ ), where 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;

F: 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 or an inert functional group, including a C ₁ -C ₃₀ hydrocarbon group, a C ₁ -C ₃₀ substituted hydrocarbon group or an inert functional group;

Y, Z: 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;

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

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

-: Refers to covalent bond or ionic bond;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , R 12 ^, R 13 , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , ^{R 21} , R ²² , R ²³ , R ²⁴ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R 32 , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁸ , ^{R 39 :} hydrogen, C ₁ -C ₃₀ hydrocarbon groups, halogen atoms, C ₁ -C ₃₀ substituted hydrocarbon groups especially refer to halogenated hydrocarbon groups, such as -CH ₂ Cl, -CH ₂ CH ₂ Cl or inert functional groups, the above groups can be the same or Can be different, wherein adjacent groups such as R ¹ and R ² , R ³ , R ³ and R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ²³ and R ²⁴ or R ²⁵ and R ²⁶ can be mutually Bonded into a ring.

R ⁵ refers to the lone pair of electrons on nitrogen, hydrogen, C ₁ -C ₃₀ hydrocarbon groups, C ₁ -C ₃₀ substituted hydrocarbon groups, oxygen-containing groups include hydroxyl, alkoxy-OR ³⁴ , and alkyl groups with ether groups include -T-OR ³⁴ , sulfur groups include -SR ³⁵ , -T-SR ³⁵ , nitrogen groups include -NR ²³ R ²⁴ , -T-NR ²³ R ²⁴ , phosphorus groups include -PR ²⁸ R ²⁹ , -T-PR ²⁸ R ²⁹ , -TP(O)R ³⁰ R ³¹ ; when R ⁵ is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group, R N, O, S, P, and Se in ⁵ can also participate in the coordination with metals.

T: is a C ₁ -C ₃₀ hydrocarbon group or a C ₁ -C ₃₀ substituted hydrocarbon group or an inert functional group;

For example, the following non-metallocene olefin polymerization catalysts:

Preferred structures are non-metallocene olefin polymerization catalysts as shown in 1, 3, 6, 16, 23. The most preferred structure is a non-metallocene olefin polymerization catalyst as shown in 1 or 6.

The non-metallocene olefin polymerization catalyst is dissolved in a solvent, and is contacted with a composite carrier or a modified composite phase by a solution impregnation method or an equal volume impregnation method to prepare a composite carrier-loaded non-metallocene olefin polymerization catalyst. The contact mentioned here refers to either adding the fluid carrier to the solution of the non-metallocene olefin polymerization catalyst, or adding the solution of the non-metallocene olefin polymerization catalyst to the fluid carrier. Then react under stirring conditions. The reaction temperature is not strictly limited in this patent, and the optional temperature is between 0°C and 100°C, preferably between 20°C and 60°C. The equal-volume impregnation process is to dissolve the non-metallocene catalyst in the solvent corresponding to the saturated adsorption of the carrier, seal the reaction for 12-72 hours, and then pump it dry. The equal-volume impregnation method requires a solvent with extremely high solubility for the non-metallocene olefin polymerization catalyst, and in the present invention, tetrahydrofuran solvent is preferred.

The above-mentioned chemical treatment process of the carrier and the loading process of the non-metallocene olefin polymerization catalyst need to be carried out under strict anhydrous and oxygen-free conditions. The anhydrous and oxygen-free conditions mentioned here refer to the content of water and oxygen in the system Continuously less than 10ppm, anhydrous and oxygen-free conditions are one of the key factors to obtain highly active supported catalysts.

The process of fully washing, filtering, drying and pumping is also the key to obtain polymers with high activity and good particle shape. The washing and filtering process removes the free substances, and drying and pumping can obtain good binding force of the reaction substances.

According to the supported non-metallocene olefin polymerization catalyst described in the present invention as the main catalyst, aluminum alkyl, aluminoxane or Lewis acid, borofluorocarbon, alkyl boron, alkyl boron ammonium salt are co-catalysts, and the reaction is carried out sufficiently Under certain conditions, carry out C2～C10 olefin slurry polymerization, gas phase polymerization, emulsion polymerization, solution polymerization or copolymerization.

The C2～C10 olefin used in the polymer prepared by the method of the present invention is selected from ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1 -octene, 1-decene, 1-undecene, 1-dodecene, 1-cyclopentene, norbornene, norbornadiene, or styrene, 1,4 butadiene, 2,5 - Homopolymerization and copolymerization of pentadiene, 1,6-hexadiene, or organic monomers containing functional groups, such as vinyl acetate, methyl acrylate, ethyl acrylate, and butyl acrylate.

Polymerization can be carried out using known techniques in the art, preferably slurry polymerization and gas phase polymerization. Polymerization of monomers and/or comonomers and supported non-metallocene olefin polymerization catalysts can be carried out at -40°C to 120°C, normal pressure to 10MPa The down contacting is carried out continuously or intermittently. Slurry polymerization is most preferred, especially for the polymerization and copolymerization of ethylene, or ethylene with other olefins, organic monomers containing functional groups.

In the slurry polymerization process, the polymerization solvent can be selected from the solvents mentioned in the above loading process, preferably hexane solvent.

Alkyl aluminum, aluminoxane or Lewis acid, borofluoroalane, alkyl boron, and alkyl boron ammonium salt can be used as cocatalysts in this polymerization system. Alkyl aluminum and aluminoxane have been described in detail above, while Lewis acid, borofluorone, alkyl boron, and alkyl boron ammonium salt then refer to the compound with the following general formula (V):

[LH] ⁺ [NE ₄ ] ^- or [L] ⁺ [NE ₄ ] ^-

Wherein L is a neutral or positive ionic Lewis acid, H is a hydrogen atom, N is aluminum or boron, each E can be the same or different, and is an aryl group with 6 to 12 carbon atoms, wherein more than one hydrogen is replaced by Halogen atom, alkoxy or phenoxy substituted. Including trimethylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, tributylammoniumtetrakis(pentafluoroboryl)boron, trimethylphosphinetetraphenylboron, trimethylammoniumtetraphenylboron Phenyl aluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o, p-dimethylphenyl)aluminum, tributylammonium tetra( p-trifluoromethylphenyl)aluminum, trimethylammonium tetrakis(p-trifluoromethylphenyl)aluminum, tributylammonium tetrakis(pentafluorophenyl)aluminum, N,N-diethylaniline tetrakis Phenylaluminum, N,N-ethylaniline tetrakis(pentafluorophenyl)aluminum, diethylammonium tetrakis(pentafluorophenyl)aluminum, etc.

The cocatalyst is preferably aluminoxane, most preferably methylalumoxane.

The conditions sufficient to carry out the polymerization reaction mentioned here refer to temperature conditions, pressure conditions, and stirring speed conditions for slurry polymerization reactions.

If necessary, hydrogen can be added as a polymer molecular weight regulator, and its partial pressure accounts for 0.01-5% of the polymer monomer pressure, preferably 0.1%-2%.

The polymerization reaction pressure is 0.1-10 MPa, preferably 0.5-4 MPa, most optimally 1-3 MPa. An increase in the polymerization pressure increases the heat capacity of the gas, thereby facilitating heat transfer during the reaction.

The polymer melting point was measured on a TA-Q100 differential scanning calorimeter (DSC) with a heating rate of 5°C/min and a temperature range of 20-200°C.

Polymer particle size distribution was measured on a Beckman Coulter LS230 laser particle size analyzer.

Example 1

1.1 Preparation of supported catalyst

1.1.1 Activation of the carrier

Take ES70 type silica gel (product of Crosfield Company) and bake it under nitrogen atmosphere. The calcination conditions are: heating rate 5°C/Min, constant temperature at 200°C for 0.5h, constant temperature at 400°C for 0.5h, then constant temperature at 600°C for 4h, and finally natural cooling under nitrogen atmosphere. Recorded as ES70-650 carrier.

1.1.2 Preparation of anhydrous magnesium chloride

Anhydrous magnesium chloride is obtained by calcining analytically pure magnesium chloride at 500°C for 3 hours in an air atmosphere.

1.1.3 Preparation of composite carrier

Under an anhydrous and oxygen-free nitrogen atmosphere (both water and oxygen content are lower than 5ppm), weigh 1.064g of anhydrous magnesium chloride, add 30ml of tetrahydrofuran (THF), stir at 30°C for 16h, and then dropwise add 2.5ml of absolute ethanol (4A molecular sieve soaked for more than 4 days), after adding 530mg ES70-650 carrier, stirring at 25°C for 4h, filtering, washing with 4×30ml toluene, filtering, and finally drying and pumping dry.

1.1.4 Preparation of modified composite carrier

Weigh 510mg composite carrier, add 20mg toluene to form a suspension, add dropwise 1ml methylaluminoxane (MAO, concentration is 1.5wt%, Witco company product, referred to as dilute MAO) and 2.5ml titanium tetrachloride hexane The solution (5% by volume, 0.41 mol/L titanium content) was stirred for 2 h, washed with 4×30 ml of toluene, filtered, finally dried and sucked dry.

1.1.5 Catalyst loading

Weigh 50 mg of the non-metallocene olefin polymerization catalyst represented by structural formula (6), add it into 20 ml of toluene, stir and dissolve at 25° C., then add it into the modified composite carrier, and stir for 16 h.

Then, it was washed with 4×30 ml of toluene, filtered, dried and sucked dry to obtain a dry, flowable, orange-red supported catalyst.

1.2 Aggregation

In the 0.5L autoclave that has been purged with dry nitrogen, add simultaneously the toluene solution of 13.5mg supported catalyst, 3ml MAO (concentration is 15wt%, be referred to as concentrated MAO) and 250ml hexane solvent, at ethylene pressure 3.0 MPa, the stirring speed is 600rpm, and the constant temperature is 50°C, and the ethylene polymerization is carried out, and the reaction time is 1h. The polymer was removed and dried to remove the solvent.

Yield: 32.7 g, polyethylene melting point 142.80°C.

Example 2

2.1 Preparation of catalyst

The preparation process of the catalyst is similar to Example 1.1. Take 507 mg of the composite carrier in 1.1.3, and only slowly add 5 ml of TiCl ₄ hexane solution dropwise. Solution impregnation was carried out in 70 mg of non-metallocene olefin polymerization catalyst in 25 ml of toluene solution, and finally washed, filtered, dried and sucked dry.

2.2 Aggregation

12 mg of supported catalyst, 3 ml of concentrated MAO, and 250 ml of hexane solvent were simultaneously added into a 0.5 L autoclave, and ethylene polymerization was carried out at an ethylene pressure of 3.0 MPa. The stirring speed is 540rpm, the reaction temperature is 60°C, and the reaction time is 1.5h.

Yield: 61.52 g.

(Remove) 35.3mg of supported catalyst, 3ml of concentrated MAO and 580ml of hexane solvent were simultaneously added to a 2L autoclave, and ethylene polymerization was carried out at an ethylene pressure of 2.0MPa. The stirring speed is 300 rpm, the reaction temperature is 50° C., and the reaction time is 1 h.

Yield: 45.6 g.

2.3 Copolymerization

24.3mg of supported catalyst, 3ml of concentrated MAO and 550ml of hexane solvent were simultaneously added into a 2L autoclave, and the stirring speed was turned on at 300rpm. At 60°C, ethylene and butene were mixed at a mass ratio of 20:1, and then the interpolymer was supplied into an autoclave, and the pressure in the autoclave was maintained at 1.3 MPa. The reaction temperature is 50° C., and the reaction time is 1 h.

The yield was 27.5 g, and the melting point of polyethylene was 139.02°C.

Example 3

Take ES-70 silica gel and keep it at 300°C for 6 hours, and record it as E870-300 carrier.

The preparation of the catalyst is similar to Example 1.1. Among them, only 530 mg of ES70-650 was replaced with 1.0 g of ES70-300 carrier to obtain a composite carrier. Then 0.5 g of it was taken and treated with 10 ml of TiCl ₄ in hexane. Finally, 48 mg of the catalyst was weighed and dissolved in 30 ml of toluene, and the catalyst was supported by a solution impregnation method.

The polymerization process was carried out similarly to Example 1.2. With 13.6mg of supported catalyst, 3ml of concentrated MAO and 250ml of hexane solvent, ethylene polymerization was carried out at ethylene pressure of 2.0MPa, stirring speed of 510rpm and 50°C. The reaction time is 1h.

Yield: 25.18 g, polyethylene melting point 142.33°C.

Example 4

The preparation of the catalyst is similar to Example 1.1. Among them, only 530mg of E870-650 was replaced with 1.0g of ES70-650 carrier to obtain a composite carrier. Then take 0.5g and treat it with only 8ml of dilute MAO. Finally, 520 mg of the modified composite carrier was taken and impregnated with an equal volume of 111 mg of catalyst in 2 ml of THF solution.

Polymerization was carried out analogously to Example 1.2. 25.9 mg of supported catalyst, 4 ml of concentrated MAO and 250 ml of hexane solvent were simultaneously added to a 0.5 L autoclave.

Yield: 28.46 g.

Example 5

The modified composite carrier is the same as in Example 4. Finally, 492 mg of the modified composite carrier was taken, and an equal volume of 1.5 ml of THF solution of 153 mg of catalyst was impregnated.

Aggregation is performed similarly (changed to: 1). 13mg of supported catalyst, 4ml of concentrated MAO and 250ml of hexane solvent were simultaneously added into a 0.5L autoclave.

Yield: 14.51 g.

Example 6

The modified composite carrier is the same as in Example 4. Finally, 500 mg of the modified composite carrier was taken and impregnated with an equal volume of 97.5 mg of catalyst and 0.8 ml of a THF solution of TiCl ₄ (the volume content of TiCl ₄ was 2%).

Polymerization was carried out analogously to Example 1. 17mg of supported catalyst, 4ml of concentrated MAO and 250ml of hexane solvent were simultaneously added into a 0.5L autoclave, and the reaction time was 0.5h.

Yield: 31.75 g, polyethylene melting point 141.33°C.

Example 7

Weigh 1g of anhydrous magnesium chloride, add 25mlTHF and 2.5ml of absolute ethanol, after dissolving, add 2g of ES70-650 carrier, add 50ml of hexane to precipitate after 5h, wash with 4×30ml of hexane, filter, and finally dry and Drain. Weigh 0.5g composite carrier, add 20ml toluene and _5mlTiCl hexane solution (volume ratio is 5%, titanium content is 0.41mol/L), after stirring for 12h, filter, wash, dry and drain to obtain modified composite carrier, use 100mg catalyst Immerse in equal volume in 0.8mlTHF for 16h and drain.

Polymerization was carried out analogously to Example 1.2. 8.6 mg of supported catalyst, 3 ml of concentrated MAO and 250 ml of hexane solvent were simultaneously added into a 0.5 L autoclave, and the reaction time was 1 h.

Yield: 35.28 g, polyethylene melting point 141.47°C.

Example 8

Weigh 2 g of the modified composite carrier in Example 7, and continue to treat it with 8 ml of dilute MAO. Take 500 mg of this modified composite carrier, impregnate it with 97 mg of catalyst and 0.8 ml of THF in equal volume for 16 hours, and then drain it.

Polymerization was carried out analogously to Example 1. 8mg of supported catalyst, 3ml of concentrated MAO and 250ml of hexane solvent were simultaneously added into a 0.5L autoclave, and the reaction time was 40min.

Yield: 12g.

Example 9

Weigh 1g of anhydrous magnesium chloride, add 25mlTHF and 2.5ml of absolute ethanol, after dissolving, add 2g of ES70-650 carrier, add _TiCl4 hexane solution (volume ratio 1%) to make it precipitate after 5h, use 4×30ml Washed with hexane, filtered, finally dried and pumped dry. Weigh 0.5 g of the composite carrier, impregnate 125 mg of catalyst in 0.8 ml THF equal volume for 16 h, and then drain it.

Polymerization was carried out analogously to Example 1. 11.5mg of supported catalyst, 3ml of concentrated MAO and 250ml of hexane solvent were simultaneously added into a 0.5L autoclave, and the reaction time was 1.5h.

Yield: 26g

Claims (8)

1. the load method of the non-metallocene catalyst of a composite carrier load is characterized in that this method may further comprise the steps:

(1) will be under 100～1000 ℃, inert atmosphere or reduced pressure as the porosu solid of carrier, drying or roasting 1～24h carry out thermal activation;

(2) magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system and forms solution, the porosu solid with thermal activation joins in this solution again, and fully reaction forms transparent system under 0～60 ℃ of agitation condition; Washing after filtration, dry and drain after make complex carrier; Perhaps this clear solution adding non-polar organic solvent is made it precipitation and fully separate out, filtration washing, drying are drained and are made complex carrier then;

(3) non-metallocene olefin polymerization catalyst is dissolved in the polar solvent, contacts 12～72 hours after scouring filtrations, dryings with complex carrier or modification complex carrier then and drain, become load type non-metallocene catalyst.

2. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that as the porosu solid of carrier being: porous organic material, IIA, IIIA, IVA family and IVB family metal oxide are at interior inorganic oxide, and oxidation mixture and mixed oxide, or the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or clay or molecular sieve.

3. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that magnesium compound is magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium in the load method, or their mixture.

4. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that described tetrahydrofuran (THF)-pure mixed solvent is tetrahydrofuran (THF)-Fatty Alcohol(C12-C14 and C12-C18), tetrahydrofuran (THF)-cyclic alcohol or tetrahydrofuran (THF)-aromatic alcohol, tetrahydrofuran (THF)-ethanol in the process with the porosu solid of thermal activation and magnesium compound effect.

5. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that porosu solid is a silica gel, magnesium compound is a magnesium halide, and magnesium halide and silica gel mass ratio are 1: 0.1～40.

6. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that modifying complex carrier and be adopt arbitrarily can with one or more chemical reagent of complex carrier surface functional group effect.

7. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that non-metallocene olefin polymerization catalyst is dissolved in the solvent, used solvent is to dissolve the mineral oil of this non-metallocene catalyst or different liquid hydrocarbons.

8. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that described Nonmetallocene polymerizing catalyst, it is characterized in that this catalyzer has the title complex of following structure:

Wherein:

M:1,2 or 3;

Q:0 or 1;

D:0 or 1;

N:1,2,3 or 4;

M: transition metal atoms;

X: be to comprise halogen atom, hydrogen atom, C ₁-C ₃₀Alkyl and C ₁-C ₃₀Replacement alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior group, several X can be identical, also can be different, can also be each other in key Cheng Huan;

In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;

A: Sauerstoffatom, sulphur atom, selenium atom, R ²¹N or R ²¹P:

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