CN110964132B - Composite carrier segmented in-situ supported non-metallocene catalyst and preparation method thereof - Google Patents

Composite carrier segmented in-situ supported non-metallocene catalyst and preparation method thereof Download PDF

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CN110964132B
CN110964132B CN201910019291.1A CN201910019291A CN110964132B CN 110964132 B CN110964132 B CN 110964132B CN 201910019291 A CN201910019291 A CN 201910019291A CN 110964132 B CN110964132 B CN 110964132B
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containing group
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magnesium compound
titanium
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CN110964132A (en
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李传峰
汪文睿
郭峰
汪开秀
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a composite carrier segmented in-situ supported non-metallocene catalyst, a preparation method and application thereof. The preparation method of the composite carrier segmented in-situ supported non-metallocene catalyst comprises the following steps: a step of dissolving a magnesium compound in tetrahydrofuran to obtain a magnesium compound solution; a step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a mixed slurry; drying the mixed slurry, or adding a precipitant into the mixed slurry and drying the obtained solid product to obtain a composite carrier, wherein the content of tetrahydrofuran in the composite carrier is 0.10-1.00wt%; a step of treating the composite carrier with a non-metallocene ligand to obtain a modified composite carrier; and treating the modified composite carrier with a chemical treatment agent selected from IVB-group metal compounds to obtain the composite carrier segmented in-situ supported non-metallocene catalyst.

Description

Composite carrier segmented in-situ supported non-metallocene catalyst and preparation method thereof
Technical Field
The present invention relates to a non-metallocene catalyst. In particular to a composite carrier segmented in-situ supported non-metallocene catalyst, a preparation method thereof and application thereof in olefin homo-polymerization/copolymerization.
Background
The non-metallocene catalyst appearing in the middle and later stages of the 90 th century is also called a post-metallocene catalyst, the central atom of the main catalyst comprises almost all transition metal elements, cyclopentadiene (metallocene) and derivative groups thereof (indene, fluorene and the like) are not contained in the structure, and coordination atoms are oxygen, nitrogen, sulfur, phosphorus and the like, and the catalyst is characterized in that central ions have stronger electrophilicity and have a cis-alkyl or halogen metal central structure, so that olefin insertion and sigma-bond transfer are easy to carry out, the central metal is easy to alkylate, and the generation of cation active center is facilitated; the complexes formed have defined geometric configurations, stereoselectivity, electronegativity and chiral adjustability. In addition, the formed metal-carbon bond is easily polarized, which is beneficial to the polymerization of olefin. Thus, an olefin polymer having a higher molecular weight can be obtained even at a higher polymerization temperature.
However, the homogeneous olefin polymerization catalyst has the defects of short activity duration, low utilization rate of active centers (easy occurrence of bimolecular deactivation), easy kettle adhesion of the generated polymer, high aluminoxane dosage in the polymerization process (high preparation cost), and only application in solution polymerization process, and the like, and the industrial application of the homogeneous olefin polymerization catalyst is severely limited.
The olefin homo/copolymerization catalyst or the catalyst system prepared by the patent documents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 has wide olefin homo/copolymerization performance and is suitable for various polymerization processes, but the catalyst or the catalyst system disclosed in the patent document needs higher cocatalyst dosage during olefin polymerization to obtain proper olefin polymerization activity, and has a kettle sticking phenomenon in the polymerization process.
In order to overcome the defects in the homogeneous catalytic system, the common practice is to load homogeneous catalysts such as non-metallocene catalysts and the like on a carrier to prepare the supported catalyst, so that the polymerization performance of olefin and the particle morphology of the obtained polymer are improved, and more polymerization processes such as gas phase polymerization or slurry polymerization are satisfied.
The non-metallocene catalysts disclosed in patent documents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 are supported in various ways to obtain supported non-metallocene catalysts, such as patent documents CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/06501, 200510119401.X, but all of the patent documents relate to supporting a non-metallocene organic compound (or called non-metallocene catalyst or non-metallocene complex) containing a transition metal on a treated carrier, or the non-metallocene catalyst is supported in a lower amount or is not tightly combined with the carrier.
Patent document CN200510080210.7 discloses a supported vanadium non-metallocene polyolefin catalyst synthesized in situ, a preparation method and application thereof, wherein dialkyl magnesium is reacted with acyl naphthol or beta-diketone to form an acyl naphthol magnesium or beta-diketone magnesium compound, and then reacted with tetravalent vanadium chloride to form a carrier and an active catalytic component.
Patent document CN200610026765.8 discloses a single site ziegler-natta olefin polymerization catalyst. The catalyst takes salicylaldehyde or substituted salicylaldehyde derivative containing coordination groups as an electron donor, and is obtained by adding a pretreated carrier (such as silica gel), a metal compound (such as titanium tetrachloride) and the electron donor into a magnesium compound (such as magnesium chloride)/tetrahydrofuran solution, and treating.
Similarly, CN200610026766.2 discloses a class of heteroatom-containing organic compounds and their use in ziegler-natta catalysts.
Patent document CN200710162676.0 discloses a magnesium compound supported non-metallocene catalyst and a method for producing the same, which is obtained by directly contacting a non-metallocene ligand with a magnesium compound containing a catalytically active metal by an in-situ supporting method. However, the contact between the catalytic active metal and the magnesium compound means that the IVB metal compound is added into the formed magnesium compound solid (such as the magnesium compound solid or the modified magnesium compound solid), so that the contact cannot fully react between the catalytic active metal and the magnesium compound, and the obtained magnesium compound carrier containing the catalytic active metal is heterogeneous and not fully contacted and reacted among molecules, thereby limiting the full play of the action of the non-metallocene ligand added subsequently.
Similarly, patent document CN200710162667.1 discloses a magnesium compound supported non-metallocene catalyst and a method for preparing the same, which have similar problems. Which is obtained by directly contacting a catalytically active metal compound with a magnesium compound containing a non-metallocene ligand by an in situ supporting method. However, the contact means that the non-metallocene ligand solution is added to the formed magnesium compound solid (such as the magnesium compound solid or the modified magnesium compound solid), and such contact cannot achieve sufficient reaction of the non-metallocene ligand with the magnesium compound, and the obtained magnesium compound carrier containing the non-metallocene ligand is necessarily heterogeneous and is not sufficiently contacted and reacted between molecules, thereby limiting the full play of the effect of the non-metallocene ligand.
The catalyst using anhydrous magnesium chloride as a carrier shows higher catalytic activity in the olefin polymerization process, but the catalyst is very brittle and is easy to break in a polymerization reactor, so that the polymer morphology is poor. The silica supported catalyst has good flowability and can be used for gas-phase fluidized bed polymerization, but the silica supported metallocene and non-metallocene catalysts show lower catalytic activity. Therefore, if magnesium chloride and silicon dioxide are organically combined well, it is possible to prepare a catalyst with high catalytic activity, controllable particle size and good abrasion resistance.
Patent document CN200910210991.5 discloses a preparation method of a supported non-metallocene catalyst, comprising the following steps: a step of dissolving a magnesium compound and a non-metallocene ligand in a solvent to obtain a magnesium compound solution; a step of mixing the porous support, which is optionally subjected to the heat activation treatment, with the magnesium compound solution to obtain a mixed slurry; adding a precipitant into the mixed slurry to obtain a composite carrier; and a step of treating the composite carrier with a chemical treatment agent selected from group IVB metal compounds to obtain the supported non-metallocene catalyst.
From the above, it can be seen that the supported non-metallocene catalysts of the prior art have the general problem that heterogeneous composition and distribution formed during the preparation of the catalyst limit the catalyst polymerization product properties and its particle morphology. Furthermore, the presence of certain components during the preparation of the catalyst may also affect the activity of the final catalyst.
Thus, there is still a need for a supported non-metallocene catalyst which is simple in preparation process, suitable for industrial production, and which can overcome those problems existing in the prior art supported non-metallocene catalysts.
Disclosure of Invention
The present inventors have made intensive studies on the basis of the prior art, and have found that the aforementioned problems can be solved by using a specific preparation method for producing a composite carrier-staged in-situ supported non-metallocene catalyst, particularly by controlling the concentration of tetrahydrofuran as a solvent in a composite carrier, thereby exerting its effect in improving catalyst activity, polymer particle morphology, and the like, and have completed the present invention.
In the preparation method of the composite carrier segmented in-situ supported non-metallocene catalyst, proton donors (such as those conventionally used in the field) are not added. In addition, in the preparation method of the composite carrier segmented in-situ supported non-metallocene catalyst, no electron donor (commonly used electron donors known in the art include compounds such as monoesters, diesters, diethers, diketones and glycol esters) is added. In addition, in the preparation method of the composite carrier segmented in-situ supported non-metallocene catalyst, the harsh reaction requirements and reaction conditions are not required. Therefore, the preparation method of the supported catalyst is simple and is very suitable for industrial production.
Specifically, the invention relates to a preparation method of a composite carrier segmented in-situ supported non-metallocene catalyst, which comprises the following steps:
a step of dissolving a magnesium compound in tetrahydrofuran to obtain a magnesium compound solution;
a step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a mixed slurry;
a step of drying the mixed slurry, or adding a precipitant to the mixed slurry and drying the obtained solid product to obtain a composite carrier, wherein the tetrahydrofuran content in the composite carrier is 0.10 to 1.00wt%, preferably 0.15 to 0.50wt%, more preferably 0.20 to 0.40wt%;
a step of treating the composite carrier with a non-metallocene ligand to obtain a modified composite carrier; and
and treating the modified composite carrier with a chemical treatment agent selected from IVB metal compounds to obtain the composite carrier segmented in-situ supported non-metallocene catalyst.
The invention also relates to a composite carrier segmented in-situ supported non-metallocene catalyst manufactured by the preparation method and application thereof in olefin homo-polymerization/copolymerization.
Technical effects
The preparation method of the composite carrier segmented in-situ supported non-metallocene catalyst has simple and feasible process.
By adopting the preparation method of the catalyst provided by the invention, surprisingly, the catalytic activity and the bulk density of the polymer are obviously improved and the amount of the cocatalyst required in the polymerization process is lower by strictly controlling and retaining a certain tetrahydrofuran content in the composite carrier prepared after the drying step.
The composite carrier segment in-situ supported non-metallocene catalyst prepared by the invention has remarkable copolymerization effect, namely the copolymerization activity of the catalyst is higher than that of the homo-polymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, namely the particle morphology of the polymer.
The composite carrier segment in-situ supported non-metallocene catalyst provided by the invention can polymerize to obtain ultra-high molecular weight polyethylene with higher molecular weight under the condition of homo-polymerization without participation of hydrogen.
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
In the context of the present invention, unless otherwise specifically defined or the meaning is beyond the understanding of the skilled artisan, hydrocarbon or hydrocarbon derivative groups of 3 carbon atoms or more (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) have the same meaning as when the prefix "positive" is uncrowded. For example, propyl is generally understood to be n-propyl, while butyl is generally understood to be n-butyl.
In the context of the present invention, physical property values of a substance (such as boiling point) are measured values at normal temperature (25 ℃) and normal pressure (101325 Pa), unless otherwise specified.
The invention relates to a preparation method of a composite carrier segmented in-situ supported non-metallocene catalyst, which comprises the following steps: a step of dissolving a magnesium compound in tetrahydrofuran to obtain a magnesium compound solution; a step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a mixed slurry; drying the mixed slurry, or adding a precipitant into the mixed slurry and drying the obtained solid product to obtain a composite carrier, wherein the content of tetrahydrofuran in the composite carrier is 0.10-1.00wt%; a step of treating the composite carrier with a non-metallocene ligand to obtain a modified composite carrier; and treating the modified composite carrier with a chemical treatment agent selected from IVB-group metal compounds to obtain the composite carrier segmented in-situ supported non-metallocene catalyst.
The procedure for obtaining the magnesium compound solution will be specifically described below.
According to this step, a magnesium compound is dissolved in tetrahydrofuran, thereby obtaining the magnesium compound solution.
In preparing the magnesium compound solution, the ratio of the magnesium compound (solid) to tetrahydrofuran in terms of magnesium element is 1mol:0.5 to 10L, preferably 1mol:1 to 8L, more preferably 1mol: 2-6L.
According to the invention, no alcohol is used in the step of obtaining the magnesium compound solution.
The preparation time of the magnesium compound solution (i.e., the dissolution time of the magnesium compound) is not particularly limited, but is generally 0.5 to 24 hours, preferably 4 to 24 hours. During this preparation, stirring may be used to promote dissolution of the magnesium compound. The stirring may take any form, such as a stirring paddle (typically at a speed of 10 to 1000 rpm), or the like. Dissolution may be promoted by appropriate heating, as needed.
The magnesium compound is specifically described below.
According to the present invention, the term "magnesium compound" refers to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a carrier for a supported olefin polymerization catalyst, using the concept generally in the art.
According to the present invention, examples of the magnesium compound include magnesium halide, alkoxymagnesium, alkylmagnesium halide and alkylalkoxymagnesium.
Specifically, examples of the magnesium halide include magnesium chloride (MgCl) 2 ) Magnesium bromide (MgBr) 2 ) Magnesium iodide (MgI) 2 ) And magnesium fluoride (MgF) 2 ) And the like, of which magnesium chloride is preferable.
Examples of the alkoxymagnesium halide include methoxymagnesium chloride (Mg (OCH) 3 ) Cl), ethoxymagnesium chloride (Mg (OC) 2 H 5 ) Cl), magnesium chloride propoxy (Mg (OC) 3 H 7 ) Cl), magnesium n-butoxide (Mg (OC) 4 H 9 ) Cl), magnesium isobutoxy chloride (Mg (i-OC) 4 H 9 ) Cl), methoxy magnesium bromide (Mg (OCH) 3 ) Br), ethoxymagnesium bromide (Mg (OC) 2 H 5 ) Br), magnesium propoxybromide (Mg (OC) 3 H 7 ) Br), n-butoxymagnesium bromide (Mg (OC) 4 H 9 ) Br), magnesium isobutoxy bromide(Mg(i-OC 4 H 9 ) Br), magnesium methoxyiodide (Mg (OCH) 3 ) I), magnesium ethoxyiodide (Mg (OC) 2 H 5 ) I), magnesium propoxyiodide (Mg (OC) 3 H 7 ) I), magnesium n-butoxide iodide (Mg (OC) 4 H 9 ) I) and magnesium isobutoxy iodide (Mg (I-OC) 4 H 9 ) I), etc., of which methoxy magnesium chloride, ethoxy magnesium chloride and isobutoxy magnesium chloride are preferred.
Examples of the magnesium alkoxide include magnesium methoxide (Mg (OCH) 3 ) 2 ) Magnesium ethoxide (Mg (OC) 2 H 5 ) 2 ) Magnesium propoxy (Mg (OC) 3 H 7 ) 2 ) Magnesium butoxide (Mg (OC) 4 H 9 ) 2 ) Magnesium isobutoxide (Mg (i-OC) 4 H 9 ) 2 ) And 2-ethylhexyloxy magnesium (Mg (OCH) 2 CH(C 2 H 5 )C 4 H - ) 2 ) And the like, of which ethoxymagnesium and isobutoxymagnesium are preferable.
Examples of the alkyl magnesium include methyl magnesium (Mg (CH) 3 ) 2 ) Ethyl magnesium (Mg (C) 2 H 5 ) 2 ) Propyl magnesium (Mg (C) 3 H 7 ) 2 ) N-butylmagnesium (Mg (C) 4 H 9 ) 2 ) And isobutyl magnesium (Mg (i-C) 4 H 9 ) 2 ) And the like, of which ethyl magnesium and n-butyl magnesium are preferable.
Examples of the alkyl magnesium halide include methyl magnesium chloride (Mg (CH) 3 ) Cl), ethyl magnesium chloride (Mg (C) 2 H 5 ) Cl), propyl magnesium chloride (Mg (C) 3 H 7 ) Cl), n-butyl magnesium chloride (Mg (C) 4 H 9 ) Cl), isobutyl magnesium chloride (Mg (i-C) 4 H 9 ) Cl), methyl magnesium bromide (Mg (CH) 3 ) Br), ethyl magnesium bromide (Mg (C) 2 H 5 ) Br), propyl magnesium bromide (Mg (C) 3 H 7 ) Br), n-butylmagnesium bromide (Mg (C) 4 H 9 ) Br), isobutyl magnesium bromide (Mg (i-C) 4 H 9 ) Br), methyl magnesium iodide (Mg (CH) 3 ) I), ethyl magnesium iodide (Mg (C) 2 H 5 ) I), propyl magnesium iodide (Mg (C) 3 H 7 ) I), n-butyl magnesium iodide (Mg (C) 4 H 9 ) I) and magnesium isobutyl iodide (Mg (I-C) 4 H 9 ) I), etc., among which methyl magnesium chloride, ethyl magnesium chloride and isobutyl magnesium chloride are preferred.
Examples of the alkylalkoxymagnesium include methylmagnesium (Mg (OCH) 3 )(CH 3 ) Magnesium methylethoxy (Mg (OC) 2 H 5 )(CH 3 ) Magnesium methylpropionate (Mg (OC) 3 H 7 )(CH 3 ) Methyl n-butoxymagnesium (Mg (OC) 4 H 9 )(CH 3 ) Magnesium methyl isobutoxide (Mg (i-OC) 4 H 9 )(CH 3 ) Ethyl methoxymagnesium (Mg (OCH) 3 )(C 2 H 5 ) Magnesium ethyl ethoxide (Mg (OC) 2 H 5 )(C 2 H 5 ) Magnesium ethylpropoxide (Mg (OC) 3 H 7 )(C 2 H 5 ) Magnesium ethyl n-butoxide (Mg (OC) 4 H 9 )(C 2 H 5 ) Magnesium ethyl isobutoxide (Mg (i-OC) 4 H 9 )(C 2 H 5 ) Propyl methoxy magnesium (Mg (OCH) 3 )(C 3 H 7 ) Magnesium propyl ethoxy (Mg (OC) 2 H 5 )(C 3 H 7 ) Magnesium propylpropoxide (Mg (OC) 3 H 7 )(C 3 H 7 ) Propyl magnesium n-butoxide (Mg (OC) 4 H 9 )(C 3 H 7 ) Magnesium propyl isobutoxide (Mg (i-OC) 4 H 9 )(C 3 H 7 ) N-butyl methoxy magnesium (Mg (OCH) 3 )(C 4 H 9 ) N-butyl ethoxymagnesium (Mg (OC) 2 H 5 )(C 4 H 9 ) N-butyl-propoxy magnesium (Mg (OC) 3 H 7 )(C 4 H 9 ) N-butyl n-butoxymagnesium (Mg (OC) 4 H 9 )(C 4 H 9 ) N-butyl magnesium isobutoxide (Mg (i-OC) 4 H 9 )(C 4 H 9 ) Isobutyl methoxymagnesium (Mg (OCH) 3 )(i-C 4 H 9 ) Isobutyl ethoxymagnesium (Mg (OC) 2 H 5 )(i-C 4 H 9 ) Magnesium isopropoxide (Mg (OC) 3 H 7 )(i-C 4 H 9 ) Isobutyl n-butoxymagnesium (Mg (OC) 4 H 9 )(i-C 4 H 9 ) And isobutylmagnesium isobutoxide (Mg (i-OC) 4 H 9 )(i-C 4 H 9 ) Butyl ethoxy magnesium is preferred among others.
These magnesium compounds may be used alone or in combination of two or more thereof, and are not particularly limited.
When used in a plurality of mixed forms, the molar ratio between any two magnesium compounds in the magnesium compound mixture is, for example, 0.25 to 4:1, preferably 0.5 to 3:1, more preferably 1 to 2:1.
a mixed slurry is obtained by mixing the porous support with the magnesium compound solution.
According to the present invention, the mixing process of the porous support and the magnesium compound solution may be performed by a general method, and is not particularly limited. For example, the porous support may be added to the magnesium compound solution by metering at a normal temperature to the preparation temperature of the magnesium compound solution, or the magnesium compound solution may be added to the porous support by metering, and mixed for 0.1 to 8 hours, preferably 0.5 to 4 hours, and most preferably 1 to 2 hours (if necessary, with stirring).
According to the present invention, as the porous carrier, the amount is used such that the mass ratio of the magnesium compound (based on the magnesium compound solid contained in the magnesium compound solution) to the porous carrier is 1:0.1-20, preferably 1:0.5-10, more preferably 1:1-5.
According to the invention, the mixed slurry is a semi-dry system, in which no free liquid is present. Although not necessary, in order to ensure uniformity of the system, the mixed slurry is preferably subjected to closed standing for a certain period of time (2 to 48 hours, preferably 4 to 24 hours, and most preferably 6 to 18 hours) after the preparation.
The porous support is specifically described below.
According to the present invention, as the porous carrier, there may be mentioned, for example, organic or inorganic porous solids conventionally used in the art as carriers in the production of supported olefin polymerization catalysts.
Specifically, examples of the organic porous solid include olefin homo-or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, (co) polyester, (co) polyamide, vinyl chloride homo-or copolymer, acrylate homo-or copolymer, methacrylate homo-or copolymer, styrene homo-or copolymer, and the like, and partially crosslinked forms of these homo-or copolymers, among which a partially crosslinked (for example, a degree of crosslinking of at least 2% but less than 100%) styrene polymer is preferable.
According to a preferred embodiment of the present invention, it is preferable that the organic porous solid has on its surface a reactive functional group such as any one or more selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, a sulfonic acid group, a carboxyl group, an amide group, an N-monosubstituted amide group, a sulfonamide group, an N-monosubstituted sulfonamide group, a mercapto group, an imide group and a hydrazide group, wherein at least one of a carboxyl group and a hydroxyl group is preferable.
According to one embodiment of the invention, the organic porous solid is subjected to a thermal and/or chemical activation treatment prior to use.
According to the present invention, the organic porous solid may be subjected to only a thermal activation treatment before use, or may be subjected to only a chemical activation treatment before use, or may be subjected to the thermal activation treatment and the chemical activation treatment in any combination order before use, without particular limitation.
The heat activation treatment may be performed in a usual manner. Such as heat treating the organic porous solid under reduced pressure or under an inert atmosphere. The inert atmosphere as used herein means that the gas contains only very small amounts or no components that can react with the organic porous solid. Examples of the inert atmosphere include a nitrogen gas atmosphere and a rare gas atmosphere, and a nitrogen gas atmosphere is preferable. Since the organic porous solid is poor in heat resistance, the heat activation process is premised on not damaging the structure and basic composition of the organic porous solid itself. Generally, the temperature of the thermal activation is 50 to 400 ℃, preferably 100 to 250 ℃, and the thermal activation time is 1 to 24 hours, preferably 2 to 12 hours.
After thermal/chemical activation, the organic porous solid needs to be stored under positive pressure in an inert atmosphere for later use.
As the inorganic porous solid, for example, there may be mentioned refractory oxides of metals of group IIA, III A, IVA or IVB of the periodic Table of the elements (such as silica (also referred to as silica or silica gel), alumina, magnesia, titania, zirconia or thoria, etc.), or any refractory composite oxides of these metals (such as silica alumina, magnesia alumina, titania silica, titania magnesia and titania alumina, etc.), as well as clays, molecular sieves (such as ZSM-5 and MCM-41), mica, montmorillonite, bentonite and diatomaceous earth, etc. The inorganic porous solid may be an oxide formed by high-temperature hydrolysis of a gaseous metal halide or a gaseous silicon compound, such as silica gel obtained by high-temperature hydrolysis of silicon tetrachloride, alumina obtained by high-temperature hydrolysis of aluminum trichloride, or the like.
As the inorganic porous solid, silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, molecular sieves, montmorillonite and the like are preferable, and silica and montmorillonite are particularly preferable.
Suitable silicas according to the invention can be produced by conventional methods or can be any commercially available product, such as Grace 955, grace 948, grace SP9-351, grace SP9-485, grace SP9-10046, davision Syloid 245 and Aerosil812, ES70X, ES70Y, ES70W, ES757, EP10X and EP11 from Grace, and CS-2133 and MS-3040 from PQ.
According to a preferred embodiment of the present invention, the inorganic porous solid preferably has a reactive functional group such as a hydroxyl group on the surface thereof.
According to the present invention, in one embodiment, the inorganic porous solid is subjected to a thermal activation treatment and/or a chemical activation treatment prior to use.
According to the present invention, the inorganic porous solid may be subjected to only a thermal activation treatment before use, or may be subjected to only a chemical activation treatment before use, or may be subjected to the thermal activation treatment and the chemical activation treatment in any combination order before use, without particular limitation.
The heat-activation treatment may be carried out in a usual manner, such as heat-treating the inorganic porous solid under reduced pressure or an inert atmosphere. The inert atmosphere as used herein means that the gas contains only an extremely small amount or no component that can react with the inorganic porous solid. Examples of the inert atmosphere include a nitrogen gas atmosphere and a rare gas atmosphere, and a nitrogen gas atmosphere is preferable. Typically, the temperature of the thermal activation is from 200 to 800 ℃, preferably from 400 to 700 ℃, most preferably from 400 to 650 ℃, and the heating time is for example from 0.5 to 24 hours, preferably from 2 to 12 hours, most preferably from 4 to 8 hours.
After thermal/chemical activation, the inorganic porous solid needs to be stored under positive pressure in an inert atmosphere for later use.
According to the present invention, the chemical activation treatment for the organic porous solid or the inorganic porous solid may be performed in a usual manner. For example, a method of chemically activating the organic porous solid or the inorganic porous solid using a chemical activator may be mentioned.
The chemical activator will be specifically described below.
According to the invention, a group IVB metal compound is used as the chemical activator.
Examples of the group IVB metal compound include at least one selected from the group consisting of a group IVB metal halide, a group IVB metal alkyl compound, a group IVB metal alkoxide compound, a group IVB metal alkyl halide and a group IVB metal alkoxide halide.
Examples of the group IVB metal halide, the group IVB metal alkyl compound, the group IVB metal alkoxy compound, the group IVB metal alkyl halide and the group IVB metal alkoxy halide include compounds having the following general structures:
M(OR 1 ) m X n R 2 4-m－n
wherein:
m is 0, 1, 2, 3 or 4;
n is 0, 1, 2, 3 or 4;
M is a group IVB metal of the periodic Table, such as titanium, zirconium, hafnium, etc.;
x is halogen, such as F, cl, br, I, etc.; and is also provided with
R 1 And R is 2 Each independently selected from C 1-10 Alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R 1 And R is 2 May be the same or different.
Specifically, examples of the group IVB metal halide include titanium Tetrafluoride (TiF) 4 ) Titanium tetrachloride (TiCl) 4 ) Titanium tetrabromide (TiBr) 4 ) Titanium Tetraiodide (TiI) 4 )；
Zirconium tetrafluoride (ZrF) 4 ) Zirconium tetrachloride (ZrCl) 4 ) Zirconium tetrabromide (ZrBr) 4 ) Zirconium tetraiodide (ZrI) 4 )；
Hafnium tetrafluoride (HfF) 4 ) Hafnium tetrachloride (HfCl) 4 ) Hafnium tetrabromide (HfBr) 4 ) Hafnium tetraiodide (HfI) 4 )。
Examples of the group IVB metal alkyl compound include tetramethyl titanium (Ti (CH) 3 ) 4 ) Titanium tetraethyl (Ti (CH) 3 CH 2 ) 4 ) Titanium tetraisobutyl (Ti (i-C) 4 H 9 ) 4 ) Tetra-n-butyl titanium (Ti (C) 4 H 9 ) 4 ) Triethylmethyl titanium (Ti (CH) 3 )(CH 3 CH 2 ) 3 ) Diethyl dimethyl titanium (Ti (CH) 3 ) 2 (CH 3 CH 2 ) 2 ) Trimethylethyl titanium (Ti (CH) 3 ) 3 (CH 3 CH 2 ) Triisobutyl methyl titanium (Ti (CH) 3 )(i-C 4 H 9 ) 3 ) Diisobutyldimethyl titanium (Ti (CH) 3 ) 2 (i-C 4 H 9 ) 2 ) Trimethyl isobutyl titanium (Ti (CH) 3 ) 3 (i-C 4 H 9 ) Triisobutyl ethyl titanium (Ti (CH) 3 CH 2 )(i-C 4 H 9 ) 3 ) Diisobutyldiethyl titanium (Ti (CH) 3 CH 2 ) 2 (i-C 4 H 9 ) 2 ) Triethylisobutyl titanium (Ti (CH) 3 CH 2 ) 3 (i-C 4 H 9 ) Tri-n-butyl methyl titanium (Ti (CH) 3 )(C 4 H 9 ) 3 ) Di-n-butyldimethyl titanium (Ti (CH) 3 ) 2 (C 4 H 9 ) 2 ) Trimethyl n-butyl titanium (Ti (CH) 3 ) 3 (C 4 H 9 ) Tri-n-butyl methyl titanium (Ti (CH) 3 CH 2 )(C 4 H 9 ) 3 ) Di-n-butyl diethyl titanium (Ti (CH) 3 CH 2 ) 2 (C 4 H 9 ) 2 ) Triethyl n-butyl titanium (Ti (CH) 3 CH 2 ) 3 (C 4 H 9 ) Etc.;
zirconium tetramethyl (Zr (CH) 3 ) 4 ) Zirconium tetraethyl (Zr (CH) 3 CH 2 ) 4 ) Zirconium tetraisobutyl (Zr (i-C) 4 H 9 ) 4 ) Tetra-n-butylzirconium (Zr (C) 4 H 9 ) 4 ) Zirconium triethyl (Zr (CH) 3 )(CH 3 CH 2 ) 3 ) Zirconium diethyl (Zr (CH) 3 ) 2 (CH 3 CH 2 ) 2 ) Trimethylethylzirconium (Zr (CH) 3 ) 3 (CH 3 CH 2 ) Triisobutyl methyl zirconium (Zr (CH) 3 )(i-C 4 H 9 ) 3 ) Diisobutylzirconium dimethyl (Zr (CH) 3 ) 2 (i-C 4 H 9 ) 2 ) Trimethylzirconium isobutyl (Zr (CH) 3 ) 3 (i-C 4 H 9 ) Triisobutylethylzirconium (Zr (CH) 3 CH 2 )(i-C 4 H 9 ) 3 ) Diisobutyldiethylzirconium (Zr (CH) 3 CH 2 ) 2 (i-C 4 H 9 ) 2 ) Triethylisobutyl zirconium (Zr (CH) 3 CH 2 ) 3 (i-C 4 H 9 ) Tri-n-butyl methyl zirconium (Zr (CH) 3 )(C 4 H 9 ) 3 )、Di-n-butylzirconium dimethyl (Zr (CH) 3 ) 2 (C 4 H 9 ) 2 ) Trimethyl n-butyl zirconium (Zr (CH) 3 ) 3 (C 4 H 9 ) Tri-n-butyl methyl zirconium (Zr (CH) 3 CH 2 )(C 4 H 9 ) 3 ) Di-n-butyl-diethyl-zirconium (Zr (CH) 3 CH 2 ) 2 (C 4 H 9 ) 2 ) Triethyl n-butyl zirconium (Zr (CH) 3 CH 2 ) 3 (C 4 H 9 ) Etc.;
hafnium tetramethyl (Hf (CH) 3 ) 4 ) Hafnium tetraethyl (Hf (CH) 3 CH 2 ) 4 ) Hafnium tetraisobutyl (Hf (i-C) 4 H 9 ) 4 ) Tetra-n-butylhafnium (Hf (C) 4 H 9 ) 4 ) Hafnium triethylmethyl (Hf (CH) 3 )(CH 3 CH 2 ) 3 ) Hafnium dimethyl diethyl (Hf (CH) 3 ) 2 (CH 3 CH 2 ) 2 ) Trimethylhafnium ethyl (Hf (CH) 3 ) 3 (CH 3 CH 2 ) Hafnium triisobutyl (Hf (CH) 3 )(i-C 4 H 9 ) 3 ) Hafnium diisobutyldimethyl (Hf (CH) 3 ) 2 (i-C 4 H 9 ) 2 ) Trimethylhafnium isobutyl (Hf (CH) 3 ) 3 (i-C 4 H 9 ) Hafnium triisobutyl ethyl (Hf (CH) 3 CH 2 )(i-C 4 H 9 ) 3 ) Diisobutylhafnium diethyl (Hf (CH) 3 CH 2 ) 2 (i-C 4 H 9 ) 2 ) Triethylisobutylhafnium (Hf (CH) 3 CH 2 ) 3 (i-C 4 H 9 ) (1), tri-n-butylhafnium methyl (Hf (CH) 3 )(C 4 H 9 ) 3 ) Di-n-butylhafnium dimethyl (Hf (CH) 3 ) 2 (C 4 H 9 ) 2 ) Trimethyl n-butyl hafnium (Hf (CH) 3 ) 3 (C 4 H 9 ) (1), tri-n-butylhafnium methyl (Hf (CH) 3 CH 2 )(C 4 H 9 ) 3 ) Di-n-butylhafnium diethyl (Hf (CH) 3 CH 2 ) 2 (C 4 H 9 ) 2 ) Triethylhafnium n-butyl (Hf (CH) 3 CH 2 ) 3 (C 4 H 9 ) And the like.
Examples of the group IVB metal alkoxide include tetramethoxytitanium (Ti (OCH) 3 ) 4 ) Titanium tetraethoxide (Ti (OCH) 3 CH 2 ) 4 ) Titanium tetraisobutoxide (Ti (i-OC) 4 H 9 ) 4 ) Titanium tetra-n-butoxide (Ti (OC) 4 H 9 ) 4 ) Triethoxy methoxy titanium (Ti (OCH) 3 )(OCH 3 CH 2 ) 3 ) Diethoxydimethoxy titanium (Ti (OCH) 3 ) 2 (OCH 3 CH 2 ) 2 ) Trimethoxyethoxytitanium (Ti (OCH) 3 ) 3 (OCH 3 CH 2 ) Titanium triisobutoxide (Ti (OCH) 3 )(i-OC 4 H 9 ) 3 ) Diisobutoxy dimethoxy titanium (Ti (OCH) 3 ) 2 (i-OC 4 H 9 ) 2 ) Titanium trimethoxyisobutoxy (Ti (OCH) 3 ) 3 (i-OC 4 H 9 ) Titanium triisobutoxide (Ti (OCH) 3 CH 2 )(i-OC 4 H 9 ) 3 ) Diisobutoxy diethoxy titanium (Ti (OCH) 3 CH 2 ) 2 (i-OC 4 H 9 ) 2 ) Titanium triethoxy isobutoxide (Ti (OCH) 3 CH 2 ) 3 (i-OC 4 H 9 ) Titanium tri-n-butoxymethoxide (Ti (OCH) 3 )(OC 4 H 9 ) 3 ) Di-n-Butoxydimethoxy titanium (Ti (OCH) 3 ) 2 (OC 4 H 9 ) 2 ) Trimethoxy-n-butoxytitanium (Ti (OCH) 3 ) 3 (OC 4 H 9 ) Titanium tri-n-butoxymethoxide (Ti (OCH) 3 CH 2 )(OC 4 H 9 ) 3 ) di-n-Butoxydiethoxy titanium (Ti (OCH) 3 CH 2 ) 2 (OC 4 H 9 ) 2 ) Titanium n-butoxide triethoxide (Ti (OCH) 3 CH 2 ) 3 (OC 4 H 9 ) Etc.;
zirconium tetramethoxyl (Zr (OCH) 3 ) 4 ) Zirconium tetraethoxide (Zr (OCH) 3 CH 2 ) 4 ) Zirconium tetraisobutoxide (Zr (i-OC) 4 H 9 ) 4 ) Zirconium tetra-n-butoxide (Zr (OC) 4 H 9 ) 4 ) Zirconium triethoxy methoxide (Zr (OCH) 3 )(OCH 3 CH 2 ) 3 ) Zirconium dimethoxy diethoxide (Zr (OCH) 3 ) 2 (OCH 3 CH 2 ) 2 ) Zirconium trimethoxyethoxide (Zr (OCH) 3 ) 3 (OCH 3 CH 2 ) Zirconium triisobutoxide methoxide (Zr (OCH) 3 )(i-OC 4 H 9 ) 3 ) Zirconium diisobutoxide dimethoxy (Zr (OCH) 3 ) 2 (i-OC 4 H 9 ) 2 ) Zirconium trimethoxy isobutoxy (Zr (OCH) 3 ) 3 (i-C 4 H 9 ) Zirconium triisobutoxide (Zr (OCH) 3 CH 2 )(i-OC 4 H 9 ) 3 ) Zirconium diisobutoxide (Zr (OCH) 3 CH 2 ) 2 (i-OC 4 H 9 ) 2 ) Zirconium triethoxy isobutoxide (Zr (OCH) 3 CH 2 ) 3 (i-OC 4 H 9 ) Zirconium tri-n-butoxymethoxide (Zr (OCH) 3 )(OC 4 H 9 ) 3 ) Di-n-Butoxydimethoxyzirconium (Zr (OCH) 3 ) 2 (OC 4 H 9 ) 2 ) Zirconium trimethoxy-n-butoxide (Zr (OCH) 3 ) 3 (OC 4 H 9 ) Zirconium tri-n-butoxymethoxide (Zr (OCH) 3 CH 2 )(OC 4 H 9 ) 3 ) di-n-Butoxydiethoxy zirconium (Zr (OCH) 3 CH 2 ) 2 (OC 4 H 9 ) 2 ) Zirconium triethoxy n-butoxide (Zr (OCH) 3 CH 2 ) 3 (OC 4 H 9 ) Etc.;
hafnium tetramethoxyate (Hf (OCH) 3 ) 4 ) Hafnium tetraethoxide (Hf (OCH) 3 CH 2 ) 4 ) Hafnium tetra-isobutoxide (Hf (i-OC) 4 H 9 ) 4 ) Hafnium tetra-n-butoxide (Hf (OC) 4 H 9 ) 4 ) Hafnium triethoxy methoxy (Hf (OCH) 3 )(OCH 3 CH 2 ) 3 ) Hafnium dimethoxy diethoxide (Hf (OCH) 3 ) 2 (OCH 3 CH 2 ) 2 ) Hafnium trimethoxyethoxide (Hf (OCH) 3 ) 3 (OCH 3 CH 2 ) Hafnium triisobutoxide (Hf (OCH) 3 )(i-OC 4 H 9 ) 3 ) Hafnium diisobutoxide (Hf (OCH) 3 ) 2 (i-OC 4 H 9 ) 2 ) Hafnium trimethoxy isobutoxide (Hf (OCH) 3 ) 3 (i-OC 4 H 9 ) Hafnium triisobutoxide (Hf (OCH) 3 CH 2 )(i-OC 4 H 9 ) 3 ) Hafnium diisobutoxide (Hf (OCH) 3 CH 2 ) 2 (i-OC 4 H 9 ) 2 ) Hafnium triethoxy isobutoxide (Hf (OCH) 3 CH 2 ) 3 (i-C 4 H 9 ) Hafnium tri-n-butoxymethoxide (Hf (OCH) 3 )(OC 4 H 9 ) 3 ) Di-n-Butoxydimethoxy hafnium (Hf (OCH) 3 ) 2 (OC 4 H 9 ) 2 ) Hafnium trimethoxy-n-butoxide (Hf (OCH) 3 ) 3 (OC 4 H 9 ) Hafnium tri-n-butoxymethoxide (Hf (OCH) 3 CH 2 )(OC 4 H 9 ) 3 ) Hafnium di-n-butoxide (Hf (OCH) 3 CH 2 ) 2 (OC 4 H 9 ) 2 ) Hafnium triethoxy n-butoxide (Hf (OCH) 3 CH 2 ) 3 (OC 4 H 9 ) And the like.
Examples of the group IVB metal alkyl halide include trimethyltitanium chloride (TiCl (CH) 3 ) 3 ) Titanium triethylchloride (TiCl (CH) 3 CH 2 ) 3 ) Triisobutyltitanium chloride (TiCl (i-C) 4 H 9 ) 3 ) Tri-n-butyl titanium chloride (TiCl (C) 4 H 9 ) 3 ) Dimethyl titanium dichloride (TiCl) 2 (CH 3 ) 2 ) Titanium diethyl dichloride (TiCl) 2 (CH 3 CH 2 ) 2 ) Diisobutyl titanium dichloride (TiCl) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl titanium chloride (TiCl (C) 4 H 9 ) 3 ) Titanium methyl trichloride (Ti (CH) 3 )Cl 3 ) Titanium ethyl trichloride (Ti (CH) 3 CH 2 )Cl 3 ) Titanium isobutyl trichloride (Ti (i-C) 4 H 9 )Cl 3 ) N-butyl titanium trichloride (Ti (C) 4 H 9 )Cl 3 )；
Trimethyl titanium bromide (TiBr (CH) 3 ) 3 ) Triethyltitanium bromide (TiBr (CH) 3 CH 2 ) 3 ) Triisobutyl titanium bromide (TiBr (i-C) 4 H 9 ) 3 ) Tri-n-butyl titanium bromide (TiBr (C) 4 H 9 ) 3 ) Dimethyl titanium dibromide (TiBr) 2 (CH 3 ) 2 ) Titanium diethyl dibromide (TiBr) 2 (CH 3 CH 2 ) 2 ) Diisobutyl titanium dibromide (TiBr) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl titanium bromide (TiBr (C) 4 H 9 ) 3 ) Methyl titanium tribromide (Ti (CH) 3 )Br 3 ) Titanium ethyltribromide (Ti (CH) 3 CH 2 )Br 3 ) Titanium isobutyl tribromide (Ti (i-C) 4 H 9 )Br 3 ) N-butyl titanium tribromide (Ti (C) 4 H 9 )Br 3 )；
Trimethylzirconium chloride (ZrCl (CH) 3 ) 3 ) Zirconium triethyl chloride (ZrCl (CH) 3 CH 2 ) 3 ) Triisobutylzirconium chloride (ZrCl (i-C) 4 H 9 ) 3 ) Tri-n-butylzirconium chloride (ZrCl (C) 4 H 9 ) 3 ) Zirconium dimethyldichloride (ZrCl) 2 (CH 3 ) 2 ) Zirconium diethyl dichloride (ZrCl) 2 (CH 3 CH 2 ) 2 ) Diisobutylzirconium dichloride (ZrCl) 2 (i-C 4 H 9 ) 2 ) Tri-n-butylzirconium chloride (ZrCl (C) 4 H 9 ) 3 ) Zirconium methyl trichloride (Zr (CH) 3 )Cl 3 ) Zirconium ethyl trichloride (Zr (CH) 3 CH 2 )Cl 3 ) Zirconium isobutyl trichloride (Zr (i-C) 4 H 9 )Cl 3 ) N-butyl zirconium trichloride (Zr (C) 4 H 9 )Cl 3 )；
Zirconium trimethyl bromide (ZrBr (CH) 3 ) 3 ) Zirconium triethylbromide (ZrBr (CH) 3 CH 2 ) 3 ) Zirconium triisobutylbromide (ZrBr (i-C) 4 H 9 ) 3 ) Tri-n-butylzirconium bromide (ZrBr (C) 4 H 9 ) 3 ) Zirconium dimethyl dibromide (ZrBr) 2 (CH 3 ) 2 ) Zirconium diethyl bromide (ZrBr) 2 (CH 3 CH 2 ) 2 ) Diisobutyl zirconium dibromide (ZrBr) 2 (i-C 4 H 9 ) 2 ) Tri-n-butylzirconium bromide (ZrBr (C) 4 H 9 ) 3 ) Zirconium methyl tribromide (Zr (CH) 3 )Br 3 ) Zirconium ethyl tribromide (Zr (CH) 3 CH 2 )Br 3 ) Zirconium isobutyl tribromide (Zr (i-C) 4 H 9 )Br 3 ) Zirconium n-butyl tribromide (Zr (C) 4 H 9 )Br 3 )；
Hafnium trimethyl chloride (HfCl (CH) 3 ) 3 ) Hafnium triethylchloride (HfCl (CH) 3 CH 2 ) 3 ) Hafnium triisobutyl chloride (HfCl (i-C) 4 H 9 ) 3 ) Tri-n-butyl hafnium chloride (HfCl (C) 4 H 9 ) 3 ) Hafnium dimethyl dichloride (HfCl) 2 (CH 3 ) 2 ) Hafnium diethyl dichloride (HfCl) 2 (CH 3 CH 2 ) 2 ) Hafnium diisobutyl dichloride (HfCl) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl hafnium chloride (HfCl (C) 4 H 9 ) 3 ) Hafnium methyltrichloride (Hf (CH) 3 )Cl 3 ) Hafnium ethyl trichloride (Hf (CH) 3 CH 2 )Cl 3 ) Hafnium isobutyl trichloride (Hf (i-C) 4 H 9 )Cl 3 ) N-butyl hafnium trichloride (Hf (C) 4 H 9 )Cl 3 )；
Hafnium trimethyl bromide (HfBr (CH) 3 ) 3 ) Hafnium triethylbromide (HfBr (CH) 3 CH 2 ) 3 ) Hafnium triisobutyl bromide (HfBr (i-C) 4 H 9 ) 3 ) Tri-n-butyl hafnium bromide (HfBr (C) 4 H 9 ) 3 ) Hafnium dimethyl bromide (HfBr) 2 (CH 3 ) 2 ) Hafnium diethyl bromide (HfBr) 2 (CH 3 CH 2 ) 2 ) Hafnium diisobutyl dibromide (HfBr) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl hafnium bromide (HfBr (C) 4 H 9 ) 3 ) Hafnium methyl tribromide (Hf (CH) 3 )Br 3 ) Hafnium ethyltribromide (Hf (CH) 3 CH 2 )Br 3 ) Hafnium isobutyl tribromide (Hf (i-C) 4 H 9 )Br 3 ) N-butyl hafnium tribromide (Hf (C) 4 H 9 )Br 3 )。
Examples of the group IVB metal alkoxyhalides include titanium trimethoxychloride (TiCl (OCH) 3 ) 3 ) Titanium triethoxy chloride (TiCl (OCH) 3 CH 2 ) 3 ) Titanium triisobutoxide chloride (TiCl (i-OC) 4 H 9 ) 3 ) Titanium tri-n-butoxide chloride (TiCl (OC) 4 H 9 ) 3 ) Titanium dimethoxy dichloride (TiCl) 2 (OCH 3 ) 2 ) Titanium diethoxy dichloride (TiCl) 2 (OCH 3 CH 2 ) 2 ) Titanium diisobutoxide dichloride (TiCl) 2 (i-OC 4 H 9 ) 2 ) Titanium tri-n-butoxide chloride (TiCl (OC) 4 H 9 ) 3 ) Titanium methoxytrichloride (Ti (OCH) 3 )Cl 3 ) Titanium ethoxytrichloride (Ti (OCH) 3 CH 2 )Cl 3 ) Titanium isobutoxy trichloride (Ti (i-C) 4 H 9 )Cl 3 ) Titanium n-butoxide trichloride (Ti (OC) 4 H 9 )Cl 3 )；
Trimethoxytitanium bromide (TiBr (OCH) 3 ) 3 ) Titanium triethoxybromide (TiBr (OCH) 3 CH 2 ) 3 ) Titanium triisobutoxide bromide (TiBr (i-OC) 4 H 9 ) 3 )、Titanium tri-n-butoxide bromide (TiBr (OC) 4 H 9 ) 3 ) Titanium dimethoxy dibromide (TiBr) 2 (OCH 3 ) 2 ) Titanium diethoxy dibromide (TiBr) 2 (OCH 3 CH 2 ) 2 ) Titanium diisobutoxy dibromide (TiBr) 2 (i-OC 4 H 9 ) 2 ) Titanium tri-n-butoxide bromide (TiBr (OC) 4 H 9 ) 3 ) Titanium methoxytribromide (Ti (OCH) 3 )Br 3 ) Titanium ethoxytribromide (Ti (OCH) 3 CH 2 )Br 3 ) Titanium isobutoxy tribromide (Ti (i-C) 4 H 9 )Br 3 ) n-Butoxytitanium tribromide (Ti (OC) 4 H 9 )Br 3 )；
Zirconium trimethoxychloride (ZrCl (OCH) 3 ) 3 ) Zirconium triethoxy chloride (ZrCl (OCH) 3 CH 2 ) 3 ) Zirconium triisobutoxide chloride (ZrCl (i-OC) 4 H 9 ) 3 ) Zirconium tri-n-butoxide chloride (ZrCl (OC) 4 H 9 ) 3 ) Zirconium dimethoxy dichloride (ZrCl) 2 (OCH 3 ) 2 ) Zirconium diethoxy dichloride (ZrCl) 2 (OCH 3 CH 2 ) 2 ) Zirconium diisobutoxy dichloride (ZrCl) 2 (i-OC 4 H 9 ) 2 ) Zirconium tri-n-butoxide chloride (ZrCl (OC) 4 H 9 ) 3 ) Zirconium methoxytrichloride (Zr (OCH) 3 )Cl 3 ) Zirconium ethoxy trichloride (Zr (OCH) 3 CH 2 )Cl 3 ) Zirconium isobutoxy trichloride (Zr (i-C) 4 H 9 )Cl 3 ) Zirconium trichloride n-butoxy (Zr (OC) 4 H 9 )Cl 3 )；
Zirconium trimethoxybromide (ZrBr (OCH) 3 ) 3 ) Zirconium triethoxy bromide (ZrBr (OCH) 3 CH 2 ) 3 ) Zirconium triisobutoxide bromide (ZrBr (i-OC) 4 H 9 ) 3 ) Zirconium tri-n-butoxide bromide (ZrBr (OC) 4 H 9 ) 3 ) Zirconium dimethoxy dibromide (ZrBr) 2 (OCH 3 ) 2 ) Zirconium diethoxy dibromide (ZrBr) 2 (OCH 3 CH 2 ) 2 ) Zirconium diisobutoxy dibromide (ZrBr) 2 (i-OC 4 H 9 ) 2 ) Zirconium tri-n-butoxide bromide (ZrBr (OC) 4 H 9 ) 3 ) Zirconium methoxytribromide (Zr (OCH) 3 )Br 3 ) Zirconium ethoxy tribromide (Zr (OCH) 3 CH 2 )Br 3 ) Zirconium isobutoxy tribromide (Zr (i-C) 4 H 9 )Br 3 ) Zirconium tribromide of n-butoxy (Zr (OC) 4 H 9 )Br 3 )；
Hafnium trimethoxychloride (HfCl (OCH) 3 ) 3 ) Hafnium chloride triethoxide (HfCl (OCH) 3 CH 2 ) 3 ) Hafnium triisobutoxide chloride (HfCl (i-OC) 4 H 9 ) 3 ) Hafnium tri-n-butoxide chloride (HfCl (OC) 4 H 9 ) 3 ) Hafnium dimethoxy dichloride (HfCl) 2 (OCH 3 ) 2 ) Hafnium diethoxy dichloride (HfCl) 2 (OCH 3 CH 2 ) 2 ) Hafnium diisobutoxy dichloride (HfCl) 2 (i-OC 4 H 9 ) 2 ) Hafnium tri-n-butoxide chloride (HfCl (OC) 4 H 9 ) 3 ) Hafnium methoxytrichloride (Hf (OCH) 3 )Cl 3 ) Hafnium ethoxy trichloride (Hf (OCH) 3 CH 2 )Cl 3 ) Hafnium isobutoxy trichloride (Hf (i-C) 4 H 9 )Cl 3 ) Hafnium n-butoxide trichloride (Hf (OC) 4 H 9 )Cl 3 )；
Hafnium trimethoxybromide (HfBr (OCH) 3 ) 3 ) Hafnium triethoxy bromide (HfBr (OCH) 3 CH 2 ) 3 ) Hafnium triisobutoxide bromide (HfBr (i-OC) 4 H 9 ) 3 ) Hafnium tri-n-butoxide bromide (HfBr (OC) 4 H 9 ) 3 ) Hafnium dimethoxy dibromide (HfBr) 2 (OCH 3 ) 2 ) Hafnium di-ethoxy dibromide (HfBr) 2 (OCH 3 CH 2 ) 2 ) Hafnium diisobutylbromide (HfBr) 2 (i-OC 4 H 9 ) 2 ) Hafnium tri-n-butoxide bromide (HfBr (OC) 4 H 9 ) 3 ) Hafnium methoxytribromide (Hf (OCH) 3 )Br 3 ) Hafnium ethoxy tribromide (Hf (OCH) 3 CH 2 )Br 3 ) Hafnium isobutoxy tribromide (Hf (i-C) 4 H 9 )Br 3 ) Hafnium n-butoxide tribromide (Hf (OC) 4 H 9 )Br 3 )。
As the group IVB metal compound, the group IVB metal halide is preferable, and TiCl is more preferable 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、HfCl 4 And HfBr 4 TiCl is most preferred 4 And ZrCl 4 。
These group IVB metal compounds may be used singly or in combination of plural kinds in any ratio.
When the chemical activator is in a liquid state at normal temperature, the chemical activator may be used by directly dropping a predetermined amount of the chemical activator into an organic porous solid or an inorganic porous solid to be activated with the chemical activator.
When the chemical activator is solid at ordinary temperature, it is preferable to use the chemical activator in the form of a solution for the convenience of metering and handling. Of course, when the chemical activator is in a liquid state at normal temperature, the chemical activator may be used in a solution form as needed, and is not particularly limited.
In preparing the solution of the chemical activator, the solvent used at this time is not particularly limited as long as it can dissolve the chemical activator.
Specifically, C may be mentioned 5-12 Alkanes, C 5-12 Cycloalkane, halogenated C 5-12 Alkanes, halogenated C 5-12 Cycloalkane, C 6-12 Aromatic hydrocarbons or halogenated C 6-12 Examples of aromatic hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, toluene, ethylbenzene, xylene, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, and the like,Chlorotoluene, chloroethylbenzene, chloroxylenes, etc., with pentane, hexane, decane, cyclohexane, and toluene being preferred, hexane and toluene being most preferred.
These solvents may be used alone or in combination of plural kinds in an arbitrary ratio.
In addition, the concentration of the chemical activator in the solution thereof is not particularly limited, and may be appropriately selected as required, as long as it can achieve the chemical activation with a predetermined amount of the chemical activator. As described above, if the chemical activator is in a liquid state, the chemical activator may be used as it is, but it may be used after being prepared into a chemical activator solution.
Conveniently, the molar concentration of the chemical activator in the solution thereof is generally set to 0.01 to 1.0mol/L, but is not limited thereto.
As a method for performing the chemical activation, for example, in the case where a chemical activator is in a solid state (such as zirconium tetrachloride), a solution of the chemical activator is first prepared, and then the solution containing a predetermined amount of the chemical activator is added (preferably dropwise) to an organic porous solid or an inorganic porous solid to be activated to perform a chemical activation reaction. In the case where the chemical activator is in a liquid state (such as titanium tetrachloride), a predetermined amount of the chemical activator may be directly added (preferably dropwise) to the organic porous solid or inorganic porous solid to be activated to perform the chemical activation reaction, or after the chemical activator is prepared as a solution, the solution containing a predetermined amount of the chemical activator may be added (preferably dropwise) to the organic porous solid or inorganic porous solid to be activated to perform the chemical activation reaction.
In general, the chemical activation reaction (if necessary with stirring) is carried out at a reaction temperature of-30 to 60 ℃ (preferably-20 to 30 ℃) for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours.
After the chemical activation reaction is finished, the chemically activated organic porous solid or inorganic porous solid can be obtained through filtration, washing and drying.
According to the present invention, the filtration, washing and drying may be performed using a conventional method, wherein the washing solvent may be the same solvent as used in dissolving the chemical activator. If necessary, the washing is generally carried out 1 to 8 times, preferably 2 to 6 times, and most preferably 2 to 4 times.
The drying may be performed by a conventional method such as an inert gas drying method, a vacuum drying method or a vacuum heating drying method, preferably an inert gas drying method or a vacuum heating drying method, and most preferably a vacuum heating drying method. The drying temperature is generally in the range of normal temperature to 140 ℃, and the drying time is generally 2-20 hours, but is not limited thereto.
According to the present invention, the surface area of the porous support is not particularly limited, but is generally 10 to 1000m 2 Preferably 100 to 600m 2 /g; the pore volume (measured by nitrogen adsorption) of the porous carrier is generally 0.1-4 cm 3 Preferably 0.2 to 2cm 3 And its average particle diameter (measured by a laser particle sizer) is preferably 1 to 500mm, more preferably 1 to 100mm.
According to the invention, the porous support may be in any form, such as a micro-powder, a granulate, a sphere, an aggregate or other form.
The composite carrier is obtained by metering a precipitant into the mixed slurry, precipitating solid matter from the mixed slurry and drying the resulting solid product. Alternatively, the composite carrier is obtained by directly drying the mixed slurry.
The precipitant is specifically described below.
According to the present invention, the term "precipitant" is used in the general sense of the art to refer to a chemically inert liquid phase which is capable of reducing the solubility of a solute (such as the magnesium compound) in its solution and thus allowing it to precipitate out of the solution in solid form.
According to the present invention, examples of the precipitant include solvents that are poor solvents for the magnesium compound and good solvents for tetrahydrofuran for dissolving the magnesium compound, such as alkanes, cycloalkanes, haloalkanes, and halocycloalkanes.
Examples of the alkane include pentane, hexane, heptane, octane, nonane, and decane, and among them, hexane, heptane, and decane are preferable, and hexane and decane are most preferable.
Examples of the cycloalkane include cyclohexane, cyclopentane, cycloheptane, cyclodecane, and cyclononane, and cyclohexane is most preferable.
Examples of the halogenated alkane include methylene chloride, dichlorohexane, dichloroheptane, chloroform, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, and tribromobutane.
Examples of the halogenated cycloalkanes include chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane.
These precipitants may be used alone or in combination of two or more kinds in any ratio.
The precipitant may be added in one-time or dropwise, preferably in one-time. During this precipitation process, agitation may be used to facilitate the dispersion of the precipitant in the mixed slurry and to facilitate the final precipitation of the solid product. The stirring may take any form, such as a stirring paddle (typically at a speed of 10 to 1000 rpm), or the like.
The amount of the precipitant is not particularly limited, but generally, the ratio of the precipitant to tetrahydrofuran for dissolving the magnesium compound is 1:0.2 to 5, preferably 1:0.5 to 2, more preferably 1:0.8 to 1.5.
The temperature of the precipitating agent is not particularly limited, but is generally preferably at ordinary temperature. Moreover, the precipitation process is also generally preferably carried out at normal temperature.
After complete precipitation, the solid product obtained is filtered, optionally washed and dried, so that a composite carrier can be obtained. The method of filtration and washing is not particularly limited, and those conventionally used in the art can be used as required.
The washing is generally carried out 1 to 6 times, preferably 2 to 3 times, as required. Among them, the same solvent as the precipitant is preferably used for the washing solvent, but may be different.
The method of drying is not particularly limited as long as the method is a drying method in which the tetrahydrofuran content in the composite carrier is controlled to be in the range of 0.10 to 1.00wt%, preferably 0.15 to 0.50wt%, more preferably 0.20 to 0.40wt% by drying the mixed slurry or by drying the solid product (optionally after washing).
According to the present invention, the drying may be performed by a conventional method such as an inert gas drying method, a vacuum drying method or a vacuum heating drying method, preferably an inert gas drying method or a vacuum heating drying method, and most preferably a vacuum heating drying method.
According to the invention, the drying mode (including drying temperature, drying vacuum degree and drying time) is limited by the tetrahydrofuran content in the composite carrier meeting the requirements of the invention. For example, the composite carrier is obtained by drying the mixed slurry at 15 to 60 ℃, preferably 35 to 55 ℃, under vacuum of 2 to 100mBar, preferably 5 to 50mBar, for 2 to 48 hours, preferably 4 to 24 hours, and then at 65 to 120 ℃, preferably 80 to 110 ℃, under vacuum of 2 to 100mBar, preferably 5 to 50mBar, for 1 to 24 hours, preferably 2 to 12 hours, in absolute pressure. Alternatively, a precipitant is added to the mixed slurry, and the obtained solid product (optionally after washing) is dried under vacuum of 2 to 100mBar, preferably 5 to 50mBar, absolute pressure at 15 to 60 ℃, preferably 35 to 55 ℃ for 2 to 48 hours, preferably 4 to 24 hours, and then dried under vacuum of 2 to 100mBar, preferably 5 to 50mBar, absolute pressure at 65 to 120 ℃, preferably 80 to 110 ℃ for 1 to 24 hours, preferably 2 to 12 hours, thereby obtaining the composite carrier.
According to the present invention, the term "non-metallocene complex" is a single-site olefin polymerization catalyst with respect to a metallocene catalyst, which does not contain cyclopentadienyl groups such as a metallocene ring, fluorene ring or indene ring or derivatives thereof in the structure, and which is capable of exhibiting olefin polymerization catalytic activity when combined with a cocatalyst such as those described below (thus the non-metallocene complex is sometimes also referred to as a non-metallocene olefin polymerizable complex). The compound comprises a central metal atom and at least one multidentate ligand (preferably a tridentate ligand or more) bound to the central metal atom in a coordination bond, and the term "non-metallocene ligand" is the aforementioned multidentate ligand.
According to the invention, the non-metallocene ligand is selected from compounds having the following chemical formula:
according to the present invention, the groups A, D and E (coordinating groups) in the compound form a coordination bond by the coordination reaction of the coordinating atoms (e.g., N, O, S, se and P heteroatoms) contained therein with the group IVB metal atoms contained in the group IVB metal compound used as the chemical treating agent in the present invention, thereby forming a complex having the group IVB metal atom as the central metal atom M (i.e., the non-metallocene complex of the present invention).
In a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (a) and (B) having the following chemical formulas:
in a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (A-1) to (A-4) and compounds (B-1) to (B-4) having the following chemical structural formula:
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in all of the above chemical structural formulas,
q is 0 or 1;
d is 0 or 1;
a is selected from oxygen atom, sulfur atom, selenium atom,-NR 23 R 24 、-N(O)R 25 R 26 、/>-PR 28 R 29 、-P(O)R 30 OR 31 Of sulfone, sulfoxide or-Se (O) R 39 Wherein N, O, S, se and P are each an atom for coordination;
b is selected from nitrogen atom, nitrogen-containing group, phosphorus-containing group or C 1 －C 30 A hydrocarbon group;
d is selected from nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing group, C 1 －C 30 A hydrocarbyl, sulfone, or sulfoxide group, wherein N, O, S, se and P are each a coordinating atom;
e is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, or a cyano group (-CN), wherein N, O, S, se and P are each a coordinating atom;
f is selected from a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, or a phosphorus-containing group, wherein N, O, S, se and P are each a coordinating atom;
G is selected from C 1 －C 30 Hydrocarbyl, substituted C 1 －C 30 Hydrocarbon or inert functional groups;
y is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, or a phosphorus-containing group, wherein N, O, S, se and P are each an atom for coordination;
z is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, and a cyano groupCN), for example, there may be mentioned-NR 23 R 24 、-N(O)R 25 R 26 、-PR 28 R 29 、-P(O)R 30 R 31 、-OR 34 、-SR 35 、-S(O)R 36 、-SeR 38 or-Se (O) R 39 Wherein N, O, S, se and P are each an atom for coordination;
-represents a single bond or a double bond;
-represents a covalent bond or an ionic bond.
R 1 To R 4 、R 6 To R 21 Each independently selected from hydrogen, C 1 －C 30 Hydrocarbyl, substituted C 1 －C 30 Hydrocarbyl (of which halogenated hydrocarbyl groups such as-CH are preferred 2 Cl and-CH 2 CH 2 Cl) or inert functional groups. R is R 22 To R 36 、R 38 And R is 39 Each independently selected from hydrogen, C 1 －C 30 Hydrocarbyl or substituted C 1 －C 30 Hydrocarbyl (of which halogenated hydrocarbyl groups such as-CH are preferred 2 Cl and-CH 2 CH 2 Cl). The above groups may be the same or different from each other, wherein adjacent groups such as R 1 And R is R 2 ，R 6 And R is R 7 ，R 7 And R is R 8 ，R 8 And R is R 9 ，R 13 And R is R 14 ，R 14 And R is R 15 ，R 15 And R is R 16 ，R 18 And R is R 19 ，R 19 And R is R 20 ，R 20 And R is R 21 ，R 23 And R is R 24 Or R 25 And R is R 26 Etc. may be bonded to each other to form a bond or a ring, preferably an aromatic ring, such as an unsubstituted benzene ring or a ring having 1 to 4C 1 －C 30 Hydrocarbyl or substituted C 1 －C 30 Hydrocarbyl (of which halogenated hydrocarbyl groups such as-CH are preferred 2 Cl and-CH 2 CH 2 Cl) substituted benzene ring.
R 5 Selected from lone pair electrons on nitrogen, hydrogen, C 1 －C 30 Hydrocarbyl, substituted C 1 －C 30 Hydrocarbon, oxygen-containing, sulfur-containing, nitrogen-containing, selenium-containing or phosphorus-containing groupsA bolus. When R is 5 R in the case of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group 5 The N, O, S, P and Se of (a) may be used as the coordinating atom (coordinating with the central metal atom M).
In the context of the present invention, examples of inert functional groups include groups selected from the group consisting of halogen, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C 1 －C 10 Ester or nitro (-NO) 2 ) At least one of (C) and the like, but generally does not include C 1 －C 30 Hydrocarbyl and substituted C 1 －C 30 A hydrocarbon group.
In the context of the present invention, the inert functional group has the following characteristics, limited by the chemical structure of the multidentate ligand of the present invention:
(1) Does not interfere with the coordination process of the group A, D, E, F, Y or Z with the central metal atom M, and
(2) The ability to coordinate to the central metal atom M is lower than the A, D, E, F, Y and Z groups and does not displace the existing coordination of these groups to the central metal atom M.
In accordance with the invention, in all of the formulae described above, any adjacent two or more groups, such as R, as the case may be 21 With a group Z, or R 13 With a group Y, which may be bound to each other to form a ring, preferably C comprising heteroatoms from said group Z or Y 6 －C 30 Aromatic heterocyclic ring such as pyridine ring and the like, wherein the aromatic heterocyclic ring is optionally substituted with 1 or more groups selected from C 1 －C 30 Hydrocarbyl and substituted C 1 －C 30 The substituent of the hydrocarbon group is substituted.
In the context of the present invention,
the halogen is selected from F, cl, br or I. The nitrogen-containing group is selected from-NR 23 R 24 、-T-NR 23 R 24 or-N (O) R 25 R 26 . The phosphorus-containing group is selected from->-PR 28 R 29 、-P(O)R 30 R 31 or-P (O) R 32 (OR 33 ). The oxygen-containing group is selected from the group consisting of hydroxy, -OR 34 and-T-OR 34 . The sulfur-containing group is selected from the group consisting of-SR 35 、-T-SR 35 、-S(O)R 36 or-T-SO 2 R 37 . The selenium-containing group is selected from the group consisting of-Ser 38 、-T-SeR 38 、-Se(O)R 39 or-T-Se (O) R 39 . The radicals T being selected from C 1 －C 30 Hydrocarbyl or substituted C 1 －C 30 A hydrocarbon group. The R is 37 Selected from hydrogen, C 1 －C 30 Hydrocarbyl or substituted C 1 －C 30 A hydrocarbon group.
In the context of the present invention, the C 1 －C 30 The hydrocarbon radical being selected from C 1 －C 30 Alkyl (preferably C 1 －C 6 Alkyl, such as isobutyl), C 7 －C 30 Alkylaryl groups (such as tolyl, xylyl, diisobutylphenyl, and the like), C 7 －C 30 Aralkyl (e.g. benzyl), C 3 －C 30 Cyclic alkyl, C 2 －C 30 Alkenyl, C 2 －C 30 Alkynyl, C 6 －C 30 Aryl (e.g., phenyl, naphthyl, anthracenyl, etc.), C 8 －C 30 Condensed ring groups or C 4 －C 30 A heterocyclic group, wherein the heterocyclic group contains 1 to 3 hetero atoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms, such as pyridyl, pyrrolyl, furyl, thienyl, or the like.
According to the invention, in the context of the present invention, the said C, depending on the specific case of the relevant group to which it is bound 1 －C 30 Hydrocarbyl is sometimes referred to as C 1 －C 30 Hydrocarbadiyl (divalent radicals, otherwise known as C 1 －C 30 Hydrocarbylene) or C 1 －C 30 Hydrocarbon tri (trivalent groups), as will be apparent to those skilled in the art.
In the context of the present invention, the substituted C 1 －C 30 Hydrocarbyl refers to C bearing one or more inert substituents 1 －C 30 A hydrocarbon group. By inert substituents is meant that these substituents are substituted for the aforementioned coordinating groups (meaning the aforementioned groups A, D, E, F, Y and Z, or optionally also including R 5 ) The coordination process with the central metal atom M (i.e., the aforementioned group IVB metal atom) is not substantially disturbed; in other words, these substituents have no ability or opportunity (e.g., affected by steric hindrance, etc.) to undergo a coordination reaction with the IVB-group metal atom to form a coordination bond, as limited by the chemical structure of the ligand of the present invention. In general, the inert substituents are selected from halogen or C 1 －C 30 Alkyl (preferably C 1 －C 6 Alkyl groups such as isobutyl).
In the context of the present invention, the silicon-containing group is selected from the group consisting of-SiR 42 R 43 R 44 or-T-SiR 45 The method comprises the steps of carrying out a first treatment on the surface of the The germanium-containing group is selected from-GeR 46 R 47 R 48 or-T-GeR 49 The method comprises the steps of carrying out a first treatment on the surface of the The tin-containing group is selected from-SnR 50 R 51 R 52 、-T-SnR 53 or-T-Sn (O) R 54 The method comprises the steps of carrying out a first treatment on the surface of the And said R is 42 To R 54 Each independently selected from hydrogen, C as described above 1 －C 30 Hydrocarbyl or substituted C as previously described 1 －C 30 Hydrocarbyl groups, which may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a bond or a ring. Wherein the radicals T are as defined above.
Examples of the non-metallocene ligand include the following compounds:
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the non-metallocene ligand is preferably selected from the following compounds:
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the non-metallocene ligand is further preferably selected from the following compounds:
more preferably, the non-metallocene ligand is selected from the following compounds:
these non-metallocene ligands may be used singly or in combination of plural kinds in any ratio.
According to the present invention, the non-metallocene ligand is not a diether compound commonly used in the art as an electron donor compound.
The non-metallocene ligand may be manufactured according to any method known to those skilled in the art. For details of the manufacturing method, see, for example, WO03/010207 and Chinese patents ZL01126323.7 and ZL02110844.7, etc., the entire contents of which are incorporated herein by reference.
According to the invention, the non-metallocene ligands are used, if necessary, in the form of solutions for metering and ease of handling.
In preparing the solution of the non-metallocene ligand, the solvent used at this time is not particularly limited as long as the non-metallocene ligand can be dissolved and the existing support structure of the composite support is not destroyed (e.g., dissolved). Examples of the solvent include C 6-12 Aromatic hydrocarbons, halogenated C 6-12 Aromatic hydrocarbon, C 5-12 Alkanes, halogenated C 1-10 One or more of alkanes, esters, and ethers. Specific examples thereof include toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, methylene chloride, dichloroethane, ethyl acetate, tetrahydrofuran, and the like. Of these, C is preferred 6-12 Aromatic hydrocarbon, C 5-12 Alkanes, tetrahydrofuran and dichloromethane.
These solvents may be used alone or in combination of plural kinds in an arbitrary ratio.
In dissolving the non-metallocene ligand, stirring may be used as required (the stirring speed is generally 10 to 500 rpm).
According to the present invention, the proportion of the non-metallocene ligand to the solvent is generally 0.02 to 0.30 g/ml, preferably 0.05 to 0.15 g/ml, but is not limited thereto in some cases.
As a method for carrying out the treatment with the non-metallocene ligand, for example, there may be mentioned a method comprising preparing a solution of the non-metallocene ligand first, then adding the solution (preferably dropwise) to the composite support to be treated (containing a predetermined amount of the non-metallocene ligand) at a temperature of-30 to 60 ℃ (preferably-20 to 30 ℃) or adding the composite support to the solution, and carrying out a treatment reaction (with stirring if necessary) at a reaction temperature of-30 to 60 ℃ (preferably-20 to 30 ℃) for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours, followed by filtration, optional washing and drying.
According to the present invention, the filtration, washing and drying may be performed by a conventional method, wherein the washing solvent may be the same solvent as that used in dissolving the non-metallocene ligand. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times.
According to the invention, the molar ratio of the magnesium compound to the non-metallocene ligand, calculated as Mg element, is 1:0.0001-1, preferably 1:0.0002 to 0.4, more preferably 1:0.0008 to 0.2, further preferably 1:0.001-0.1.
Next, the modified composite support is treated with a chemical treatment agent selected from group IVB metal compounds, thereby obtaining the composite support segmented in situ supported non-metallocene catalyst of the present invention.
According to the present invention, by chemically treating the modified composite support with the chemical treatment agent, the chemical treatment agent can be reacted with a non-metallocene ligand contained in the modified composite support to form a non-metallocene complex in situ on the support (in situ supporting reaction), thereby obtaining the composite support-segmented in situ supported non-metallocene catalyst of the present invention.
The chemical treatment agent is specifically described below.
According to the invention, a group IVB metal compound is used as the chemical treatment agent.
Examples of the group IVB metal compound include group IVB metal halides, group IVB metal alkyls, group IVB metal alkoxides, group IVB metal alkyl halides and group IVB metal alkoxy halides.
Examples of the group IVB metal halide, the group IVB metal alkyl compound, the group IVB metal alkoxy compound, the group IVB metal alkyl halide and the group IVB metal alkoxy halide include compounds having the structure of the following general formula (IV):
M(OR 1 ) m X n R 2 4-m－n (IV)
wherein:
m is 0, 1, 2, 3 or 4;
n is 0, 1, 2, 3 or 4;
m is a group IVB metal of the periodic Table, such as titanium, zirconium, hafnium, etc.;
X is halogen, such as F, cl, br, I, etc.; and is also provided with
R 1 And R is 2 Each independently selected from C 1-10 Alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R 1 And R is 2 May be the same or different.
Specifically, examples of the group IVB metal halide include titanium Tetrafluoride (TiF) 4 ) Titanium tetrachloride (TiCl) 4 ) Titanium tetrabromide (TiBr) 4 ) Titanium Tetraiodide (TiI) 4 )；
Zirconium tetrafluoride (ZrF) 4 ) Zirconium tetrachloride (ZrCl) 4 ) Zirconium tetrabromide (ZrBr) 4 ) Zirconium tetraiodide (ZrI) 4 )；
Hafnium tetrafluoride (HfF) 4 ) Hafnium tetrachloride (HfCl) 4 ) Hafnium tetrabromide (HfBr) 4 ) Hafnium tetraiodide (HfI) 4 )。
Examples of the group IVB metal alkyl compound include tetramethyl titanium (Ti (CH) 3 ) 4 ) Titanium tetraethyl (Ti (CH) 3 CH 2 ) 4 ) Titanium tetraisobutyl (Ti (i-C) 4 H 9 ) 4 ) Tetra-n-butyl titanium (Ti (C) 4 H 9 ) 4 ) Triethylmethyl titanium (Ti (CH) 3 )(CH 3 CH 2 ) 3 ) Diethyl dimethyl titanium (Ti (CH) 3 ) 2 (CH 3 CH 2 ) 2 ) Trimethylethyl titanium (Ti (CH) 3 ) 3 (CH 3 CH 2 ) Triisobutyl methyl titanium (Ti (CH) 3 )(i-C 4 H 9 ) 3 ) Diisobutyldimethyl titanium (Ti (CH) 3 ) 2 (i-C 4 H 9 ) 2 ) Trimethyl isobutyl titanium (Ti (CH) 3 ) 3 (i-C 4 H 9 ) Triisobutyl ethyl titanium (Ti (CH) 3 CH 2 )(i-C 4 H 9 ) 3 ) Diisobutyldiethyl titanium (Ti (CH) 3 CH 2 ) 2 (i-C 4 H 9 ) 2 ) Triethylisobutyl titanium (Ti (CH) 3 CH 2 ) 3 (i-C 4 H 9 ) Tri-n-butyl methyl titanium (Ti (CH) 3 )(C 4 H 9 ) 3 ) Di-n-butyldimethyl titanium (Ti (CH) 3 ) 2 (C 4 H 9 ) 2 ) Trimethyl n-butyl titanium (Ti (CH) 3 ) 3 (C 4 H 9 ) Tri-n-butyl methyl titanium (Ti (CH) 3 CH 2 )(C 4 H 9 ) 3 ) Di-n-butyl diethyl titanium (Ti (CH) 3 CH 2 ) 2 (C 4 H 9 ) 2 ) Triethyl n-butyl titanium (Ti (CH) 3 CH 2 ) 3 (C 4 H 9 ) Etc.;
zirconium tetramethyl (Zr (CH) 3 ) 4 ) Zirconium tetraethyl (Zr (CH) 3 CH 2 ) 4 ) Zirconium tetraisobutyl (Zr (i-C) 4 H 9 ) 4 ) Tetra-n-butylzirconium (Zr (C) 4 H 9 ) 4 ) Zirconium triethyl (Zr (CH) 3 )(CH 3 CH 2 ) 3 ) Zirconium diethyl (Zr (CH) 3 ) 2 (CH 3 CH 2 ) 2 ) Trimethylethylzirconium (Zr (CH) 3 ) 3 (CH 3 CH 2 ) Triisobutyl methyl zirconium (Zr (CH) 3 )(i-C 4 H 9 ) 3 ) Diisobutylzirconium dimethyl (Zr (CH) 3 ) 2 (i-C 4 H 9 ) 2 ) Trimethylzirconium isobutyl (Zr (CH) 3 ) 3 (i-C 4 H 9 ) Triisobutylethylzirconium (Zr (CH) 3 CH 2 )(i-C 4 H 9 ) 3 ) Diisobutyldiethylzirconium (Zr (CH) 3 CH 2 ) 2 (i-C 4 H 9 ) 2 ) Triethylisobutyl zirconium (Zr (CH) 3 CH 2 ) 3 (i-C 4 H 9 ) Tri-n-butyl methyl zirconium (Zr (CH) 3 )(C 4 H 9 ) 3 ) Di-n-butylzirconium dimethyl (Zr (CH) 3 ) 2 (C 4 H 9 ) 2 ) Trimethyl n-butyl zirconium (Zr (CH) 3 ) 3 (C 4 H 9 ) Tri-n-butyl methyl zirconium (Zr (CH) 3 CH 2 )(C 4 H 9 ) 3 ) Di-n-butyl-diethyl-zirconium (Zr (CH) 3 CH 2 ) 2 (C 4 H 9 ) 2 ) Triethyl n-butyl zirconium (Zr (CH) 3 CH 2 ) 3 (C 4 H 9 ) Etc.;
hafnium tetramethyl (Hf (CH) 3 ) 4 ) Hafnium tetraethyl (Hf (CH) 3 CH 2 ) 4 ) Hafnium tetraisobutyl (Hf (i-C) 4 H 9 ) 4 ) Tetra-n-butylhafnium (Hf (C) 4 H 9 ) 4 ) Hafnium triethylmethyl (Hf (CH) 3 )(CH 3 CH 2 ) 3 ) Hafnium dimethyl diethyl (Hf (CH) 3 ) 2 (CH 3 CH 2 ) 2 ) Trimethylhafnium ethyl (Hf (CH) 3 ) 3 (CH 3 CH 2 ) Hafnium triisobutyl (Hf (CH) 3 )(i-C 4 H 9 ) 3 ) Hafnium diisobutyldimethyl (Hf (CH) 3 ) 2 (i-C 4 H 9 ) 2 ) Trimethylhafnium isobutyl (Hf (CH) 3 ) 3 (i-C 4 H 9 ) Hafnium triisobutyl ethyl (Hf (CH) 3 CH 2 )(i-C 4 H 9 ) 3 ) Diisobutylhafnium diethyl (Hf (CH) 3 CH 2 ) 2 (i-C 4 H 9 ) 2 ) Triethylisobutylhafnium (Hf (CH) 3 CH 2 ) 3 (i-C 4 H 9 ) (1), tri-n-butylhafnium methyl (Hf (CH) 3 )(C 4 H 9 ) 3 ) Di-n-butylhafnium dimethyl (Hf (CH) 3 ) 2 (C 4 H 9 ) 2 ) Trimethyl n-butyl hafnium (Hf (CH) 3 ) 3 (C 4 H 9 ) (1), tri-n-butylhafnium methyl (Hf (CH) 3 CH 2 )(C 4 H 9 ) 3 ) Di-n-butylhafnium diethyl (Hf (CH) 3 CH 2 ) 2 (C 4 H 9 ) 2 ) Triethylhafnium n-butyl (Hf (CH) 3 CH 2 ) 3 (C 4 H 9 ) And the like.
As the group IVB metal alkoxide, for example, it is possible toFor example, tetramethoxytitanium (Ti (OCH) 3 ) 4 ) Titanium tetraethoxide (Ti (OCH) 3 CH 2 ) 4 ) Titanium tetraisobutoxide (Ti (i-OC) 4 H 9 ) 4 ) Titanium tetra-n-butoxide (Ti (OC) 4 H 9 ) 4 ) Triethoxy methoxy titanium (Ti (OCH) 3 )(OCH 3 CH 2 ) 3 ) Diethoxydimethoxy titanium (Ti (OCH) 3 ) 2 (OCH 3 CH 2 ) 2 ) Trimethoxyethoxytitanium (Ti (OCH) 3 ) 3 (OCH 3 CH 2 ) Titanium triisobutoxide (Ti (OCH) 3 )(i-OC 4 H 9 ) 3 ) Diisobutoxy dimethoxy titanium (Ti (OCH) 3 ) 2 (i-OC 4 H 9 ) 2 ) Titanium trimethoxyisobutoxy (Ti (OCH) 3 ) 3 (i-OC 4 H 9 ) Titanium triisobutoxide (Ti (OCH) 3 CH 2 )(i-OC 4 H 9 ) 3 ) Diisobutoxy diethoxy titanium (Ti (OCH) 3 CH 2 ) 2 (i-OC 4 H 9 ) 2 ) Titanium triethoxy isobutoxide (Ti (OCH) 3 CH 2 ) 3 (i-OC 4 H 9 ) Titanium tri-n-butoxymethoxide (Ti (OCH) 3 )(OC 4 H 9 ) 3 ) Di-n-Butoxydimethoxy titanium (Ti (OCH) 3 ) 2 (OC 4 H 9 ) 2 ) Trimethoxy-n-butoxytitanium (Ti (OCH) 3 ) 3 (OC 4 H 9 ) Titanium tri-n-butoxymethoxide (Ti (OCH) 3 CH 2 )(OC 4 H 9 ) 3 ) di-n-Butoxydiethoxy titanium (Ti (OCH) 3 CH 2 ) 2 (OC 4 H 9 ) 2 ) Titanium n-butoxide triethoxide (Ti (OCH) 3 CH 2 ) 3 (OC 4 H 9 ) Etc.;
zirconium tetramethoxyl (Zr (OCH) 3 ) 4 ) Zirconium tetraethoxide (Zr (OCH) 3 CH 2 ) 4 ) Zirconium tetraisobutoxide (Zr (i-OC) 4 H 9 ) 4 ) Zirconium tetra-n-butoxide (Zr)(OC 4 H 9 ) 4 ) Zirconium triethoxy methoxide (Zr (OCH) 3 )(OCH 3 CH 2 ) 3 ) Zirconium dimethoxy diethoxide (Zr (OCH) 3 ) 2 (OCH 3 CH 2 ) 2 ) Zirconium trimethoxyethoxide (Zr (OCH) 3 ) 3 (OCH 3 CH 2 ) Zirconium triisobutoxide methoxide (Zr (OCH) 3 )(i-OC 4 H 9 ) 3 ) Zirconium diisobutoxide dimethoxy (Zr (OCH) 3 ) 2 (i-OC 4 H 9 ) 2 ) Zirconium trimethoxy isobutoxy (Zr (OCH) 3 ) 3 (i-C 4 H 9 ) Zirconium triisobutoxide (Zr (OCH) 3 CH 2 )(i-OC 4 H 9 ) 3 ) Zirconium diisobutoxide (Zr (OCH) 3 CH 2 ) 2 (i-OC 4 H 9 ) 2 ) Zirconium triethoxy isobutoxide (Zr (OCH) 3 CH 2 ) 3 (i-OC 4 H 9 ) Zirconium tri-n-butoxymethoxide (Zr (OCH) 3 )(OC 4 H 9 ) 3 ) Di-n-Butoxydimethoxyzirconium (Zr (OCH) 3 ) 2 (OC 4 H 9 ) 2 ) Zirconium trimethoxy-n-butoxide (Zr (OCH) 3 ) 3 (OC 4 H 9 ) Zirconium tri-n-butoxymethoxide (Zr (OCH) 3 CH 2 )(OC 4 H 9 ) 3 ) di-n-Butoxydiethoxy zirconium (Zr (OCH) 3 CH 2 ) 2 (OC 4 H 9 ) 2 ) Zirconium triethoxy n-butoxide (Zr (OCH) 3 CH 2 ) 3 (OC 4 H 9 ) Etc.;
hafnium tetramethoxyate (Hf (OCH) 3 ) 4 ) Hafnium tetraethoxide (Hf (OCH) 3 CH 2 ) 4 ) Hafnium tetra-isobutoxide (Hf (i-OC) 4 H 9 ) 4 ) Hafnium tetra-n-butoxide (Hf (OC) 4 H 9 ) 4 ) Hafnium triethoxy methoxy (Hf (OCH) 3 )(OCH 3 CH 2 ) 3 ) Hafnium dimethoxy diethoxide (Hf (OCH) 3 ) 2 (OCH 3 CH 2 ) 2 ) Hafnium trimethoxyethoxide (Hf (OCH) 3 ) 3 (OCH 3 CH 2 ) Hafnium triisobutoxide (Hf (OCH) 3 )(i-OC 4 H 9 ) 3 ) Hafnium diisobutoxide (Hf (OCH) 3 ) 2 (i-OC 4 H 9 ) 2 ) Hafnium trimethoxy isobutoxide (Hf (OCH) 3 ) 3 (i-OC 4 H 9 ) Hafnium triisobutoxide (Hf (OCH) 3 CH 2 )(i-OC 4 H 9 ) 3 ) Hafnium diisobutoxide (Hf (OCH) 3 CH 2 ) 2 (i-OC 4 H 9 ) 2 ) Hafnium triethoxy isobutoxide (Hf (OCH) 3 CH 2 ) 3 (i-C 4 H 9 ) Hafnium tri-n-butoxymethoxide (Hf (OCH) 3 )(OC 4 H 9 ) 3 ) Di-n-Butoxydimethoxy hafnium (Hf (OCH) 3 ) 2 (OC 4 H 9 ) 2 ) Hafnium trimethoxy-n-butoxide (Hf (OCH) 3 ) 3 (OC 4 H 9 ) Hafnium tri-n-butoxymethoxide (Hf (OCH) 3 CH 2 )(OC 4 H 9 ) 3 ) Hafnium di-n-butoxide (Hf (OCH) 3 CH 2 ) 2 (OC 4 H 9 ) 2 ) Hafnium triethoxy n-butoxide (Hf (OCH) 3 CH 2 ) 3 (OC 4 H 9 ) And the like.
Examples of the group IVB metal alkyl halide include trimethyltitanium chloride (TiCl (CH) 3 ) 3 ) Titanium triethylchloride (TiCl (CH) 3 CH 2 ) 3 ) Triisobutyltitanium chloride (TiCl (i-C) 4 H 9 ) 3 ) Tri-n-butyl titanium chloride (TiCl (C) 4 H 9 ) 3 ) Dimethyl titanium dichloride (TiCl) 2 (CH 3 ) 2 ) Titanium diethyl dichloride (TiCl) 2 (CH 3 CH 2 ) 2 ) Diisobutyl titanium dichloride (TiCl) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl titanium chloride (TiCl (C) 4 H 9 ) 3 ) Titanium methyl trichloride (Ti (CH) 3 )Cl 3 ) Titanium ethyl trichloride (Ti (CH) 3 CH 2 )Cl 3 ) Titanium isobutyl trichloride (Ti (i-C) 4 H 9 )Cl 3 ) N-butyl titanium trichloride (Ti (C) 4 H 9 )Cl 3 )；
Trimethyl titanium bromide (TiBr (CH) 3 ) 3 ) Triethyltitanium bromide (TiBr (CH) 3 CH 2 ) 3 ) Triisobutyl titanium bromide (TiBr (i-C) 4 H 9 ) 3 ) Tri-n-butyl titanium bromide (TiBr (C) 4 H 9 ) 3 ) Dimethyl titanium dibromide (TiBr) 2 (CH 3 ) 2 ) Titanium diethyl dibromide (TiBr) 2 (CH 3 CH 2 ) 2 ) Diisobutyl titanium dibromide (TiBr) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl titanium bromide (TiBr (C) 4 H 9 ) 3 ) Methyl titanium tribromide (Ti (CH) 3 )Br 3 ) Titanium ethyltribromide (Ti (CH) 3 CH 2 )Br 3 ) Titanium isobutyl tribromide (Ti (i-C) 4 H 9 )Br 3 ) N-butyl titanium tribromide (Ti (C) 4 H 9 )Br 3 )；
Trimethylzirconium chloride (ZrCl (CH) 3 ) 3 ) Zirconium triethyl chloride (ZrCl (CH) 3 CH 2 ) 3 ) Triisobutylzirconium chloride (ZrCl (i-C) 4 H 9 ) 3 ) Tri-n-butylzirconium chloride (ZrCl (C) 4 H 9 ) 3 ) Zirconium dimethyldichloride (ZrCl) 2 (CH 3 ) 2 ) Zirconium diethyl dichloride (ZrCl) 2 (CH 3 CH 2 ) 2 ) Diisobutylzirconium dichloride (ZrCl) 2 (i-C 4 H 9 ) 2 ) Tri-n-butylzirconium chloride (ZrCl (C) 4 H 9 ) 3 ) Zirconium methyl trichloride (Zr (CH) 3 )Cl 3 ) Zirconium ethyl trichloride (Zr (CH) 3 CH 2 )Cl 3 ) Zirconium isobutyl trichloride (Zr (i-C) 4 H 9 )Cl 3 ) N-butyl zirconium trichloride (Zr (C) 4 H 9 )Cl 3 )；
Zirconium trimethyl bromide (ZrBr (CH) 3 ) 3 ) Zirconium triethylbromide (ZrBr (CH) 3 CH 2 ) 3 ) Zirconium triisobutylbromide (ZrBr (i-C) 4 H 9 ) 3 ) Tri-n-butylzirconium bromide (ZrBr (C) 4 H 9 ) 3 ) Zirconium dimethyl dibromide (ZrBr) 2 (CH 3 ) 2 ) Zirconium diethyl bromide (ZrBr) 2 (CH 3 CH 2 ) 2 ) Diisobutyl zirconium dibromide (ZrBr) 2 (i-C 4 H 9 ) 2 ) Tri-n-butylzirconium bromide (ZrBr (C) 4 H 9 ) 3 ) Zirconium methyl tribromide (Zr (CH) 3 )Br 3 ) Zirconium ethyl tribromide (Zr (CH) 3 CH 2 )Br 3 ) Zirconium isobutyl tribromide (Zr (i-C) 4 H 9 )Br 3 ) Zirconium n-butyl tribromide (Zr (C) 4 H 9 )Br 3 )；
Hafnium trimethyl chloride (HfCl (CH) 3 ) 3 ) Hafnium triethylchloride (HfCl (CH) 3 CH 2 ) 3 ) Hafnium triisobutyl chloride (HfCl (i-C) 4 H 9 ) 3 ) Tri-n-butyl hafnium chloride (HfCl (C) 4 H 9 ) 3 ) Hafnium dimethyl dichloride (HfCl) 2 (CH 3 ) 2 ) Hafnium diethyl dichloride (HfCl) 2 (CH 3 CH 2 ) 2 ) Hafnium diisobutyl dichloride (HfCl) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl hafnium chloride (HfCl (C) 4 H 9 ) 3 ) Hafnium methyltrichloride (Hf (CH) 3 )Cl 3 ) Hafnium ethyl trichloride (Hf (CH) 3 CH 2 )Cl 3 ) Hafnium isobutyl trichloride (Hf (i-C) 4 H 9 )Cl 3 ) N-butyl hafnium trichloride (Hf (C) 4 H 9 )Cl 3 )；
Hafnium trimethyl bromide (HfBr (CH) 3 ) 3 ) Hafnium triethylbromide (HfBr (CH) 3 CH 2 ) 3 ) Hafnium triisobutyl bromide (HfBr (i-C) 4 H 9 ) 3 ) Tri-n-butyl hafnium bromide (HfBr (C) 4 H 9 ) 3 )、Hafnium dimethyl bromide (HfBr) 2 (CH 3 ) 2 ) Hafnium diethyl bromide (HfBr) 2 (CH 3 CH 2 ) 2 ) Hafnium diisobutyl dibromide (HfBr) 2 (i-C 4 H 9 ) 2 ) Tri-n-butyl hafnium bromide (HfBr (C) 4 H 9 ) 3 ) Hafnium methyl tribromide (Hf (CH) 3 )Br 3 ) Hafnium ethyltribromide (Hf (CH) 3 CH 2 )Br 3 ) Hafnium isobutyl tribromide (Hf (i-C) 4 H 9 )Br 3 ) N-butyl hafnium tribromide (Hf (C) 4 H 9 )Br 3 )。
Examples of the group IVB metal alkoxyhalides include titanium trimethoxychloride (TiCl (OCH) 3 ) 3 ) Titanium triethoxy chloride (TiCl (OCH) 3 CH 2 ) 3 ) Titanium triisobutoxide chloride (TiCl (i-OC) 4 H 9 ) 3 ) Titanium tri-n-butoxide chloride (TiCl (OC) 4 H 9 ) 3 ) Titanium dimethoxy dichloride (TiCl) 2 (OCH 3 ) 2 ) Titanium diethoxy dichloride (TiCl) 2 (OCH 3 CH 2 ) 2 ) Titanium diisobutoxide dichloride (TiCl) 2 (i-OC 4 H 9 ) 2 ) Titanium tri-n-butoxide chloride (TiCl (OC) 4 H 9 ) 3 ) Titanium methoxytrichloride (Ti (OCH) 3 )Cl 3 ) Titanium ethoxytrichloride (Ti (OCH) 3 CH 2 )Cl 3 ) Titanium isobutoxy trichloride (Ti (i-C) 4 H 9 )Cl 3 ) Titanium n-butoxide trichloride (Ti (OC) 4 H 9 )Cl 3 )；
Trimethoxytitanium bromide (TiBr (OCH) 3 ) 3 ) Titanium triethoxybromide (TiBr (OCH) 3 CH 2 ) 3 ) Titanium triisobutoxide bromide (TiBr (i-OC) 4 H 9 ) 3 ) Titanium tri-n-butoxide bromide (TiBr (OC) 4 H 9 ) 3 ) Titanium dimethoxy dibromide (TiBr) 2 (OCH 3 ) 2 ) Titanium diethoxy dibromide (TiBr) 2 (OCH 3 CH 2 ) 2 ) Second partTitanium dibromide isobutoxide (TiBr) 2 (i-OC 4 H 9 ) 2 ) Titanium tri-n-butoxide bromide (TiBr (OC) 4 H 9 ) 3 ) Titanium methoxytribromide (Ti (OCH) 3 )Br 3 ) Titanium ethoxytribromide (Ti (OCH) 3 CH 2 )Br 3 ) Titanium isobutoxy tribromide (Ti (i-C) 4 H 9 )Br 3 ) n-Butoxytitanium tribromide (Ti (OC) 4 H 9 )Br 3 )；
Zirconium trimethoxychloride (ZrCl (OCH) 3 ) 3 ) Zirconium triethoxy chloride (ZrCl (OCH) 3 CH 2 ) 3 ) Zirconium triisobutoxide chloride (ZrCl (i-OC) 4 H 9 ) 3 ) Zirconium tri-n-butoxide chloride (ZrCl (OC) 4 H 9 ) 3 ) Zirconium dimethoxy dichloride (ZrCl) 2 (OCH 3 ) 2 ) Zirconium diethoxy dichloride (ZrCl) 2 (OCH 3 CH 2 ) 2 ) Zirconium diisobutoxy dichloride (ZrCl) 2 (i-OC 4 H 9 ) 2 ) Zirconium tri-n-butoxide chloride (ZrCl (OC) 4 H 9 ) 3 ) Zirconium methoxytrichloride (Zr (OCH) 3 )Cl 3 ) Zirconium ethoxy trichloride (Zr (OCH) 3 CH 2 )Cl 3 ) Zirconium isobutoxy trichloride (Zr (i-C) 4 H 9 )Cl 3 ) Zirconium trichloride n-butoxy (Zr (OC) 4 H 9 )Cl 3 )；
Zirconium trimethoxybromide (ZrBr (OCH) 3 ) 3 ) Zirconium triethoxy bromide (ZrBr (OCH) 3 CH 2 ) 3 ) Zirconium triisobutoxide bromide (ZrBr (i-OC) 4 H 9 ) 3 ) Zirconium tri-n-butoxide bromide (ZrBr (OC) 4 H 9 ) 3 ) Zirconium dimethoxy dibromide (ZrBr) 2 (OCH 3 ) 2 ) Zirconium diethoxy dibromide (ZrBr) 2 (OCH 3 CH 2 ) 2 ) Zirconium diisobutoxy dibromide (ZrBr) 2 (i-OC 4 H 9 ) 2 ) Zirconium tri-n-butoxide bromide (ZrBr (OC) 4 H 9 ) 3 ) Zirconium methoxytribromide (Zr (OCH) 3 )Br 3 ) Zirconium ethoxy tribromide (Zr (OCH) 3 CH 2 )Br 3 ) Zirconium isobutoxy tribromide (Zr (i-C) 4 H 9 )Br 3 ) Zirconium tribromide of n-butoxy (Zr (OC) 4 H 9 )Br 3 )；
Hafnium trimethoxychloride (HfCl (OCH) 3 ) 3 ) Hafnium chloride triethoxide (HfCl (OCH) 3 CH 2 ) 3 ) Hafnium triisobutoxide chloride (HfCl (i-OC) 4 H 9 ) 3 ) Hafnium tri-n-butoxide chloride (HfCl (OC) 4 H 9 ) 3 ) Hafnium dimethoxy dichloride (HfCl) 2 (OCH 3 ) 2 ) Hafnium diethoxy dichloride (HfCl) 2 (OCH 3 CH 2 ) 2 ) Hafnium diisobutoxy dichloride (HfCl) 2 (i-OC 4 H 9 ) 2 ) Hafnium tri-n-butoxide chloride (HfCl (OC) 4 H 9 ) 3 ) Hafnium methoxytrichloride (Hf (OCH) 3 )Cl 3 ) Hafnium ethoxy trichloride (Hf (OCH) 3 CH 2 )Cl 3 ) Hafnium isobutoxy trichloride (Hf (i-C) 4 H 9 )Cl 3 ) Hafnium n-butoxide trichloride (Hf (OC) 4 H 9 )Cl 3 )；
Hafnium trimethoxybromide (HfBr (OCH) 3 ) 3 ) Hafnium triethoxy bromide (HfBr (OCH) 3 CH 2 ) 3 ) Hafnium triisobutoxide bromide (HfBr (i-OC) 4 H 9 ) 3 ) Hafnium tri-n-butoxide bromide (HfBr (OC) 4 H 9 ) 3 ) Hafnium dimethoxy dibromide (HfBr) 2 (OCH 3 ) 2 ) Hafnium di-ethoxy dibromide (HfBr) 2 (OCH 3 CH 2 ) 2 ) Hafnium diisobutylbromide (HfBr) 2 (i-OC 4 H 9 ) 2 ) Hafnium tri-n-butoxide bromide (HfBr (OC) 4 H 9 ) 3 ) Hafnium methoxytribromide (Hf (OCH) 3 )Br 3 ) Hafnium ethoxy tribromide (Hf (OCH) 3 CH 2 )Br 3 ) Hafnium isobutoxy tribromide (Hf (i-C) 4 H 9 )Br 3 ) Hafnium n-butoxide tribromide(Hf(OC 4 H 9 )Br 3 )。
As the group IVB metal compound, the group IVB metal halide is preferable, and TiCl is more preferable 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、HfCl 4 And HfBr 4 TiCl is most preferred 4 And ZrCl 4 。
These group IVB metal compounds may be used singly or in combination of plural kinds in any ratio.
When the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment reaction may be directly performed using the chemical treatment agent. When the chemical treatment agent is solid at ordinary temperature, it is preferable to use the chemical treatment agent in the form of a solution for the convenience of metering and handling. Of course, when the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment agent may be used in a solution form as needed, and is not particularly limited.
In preparing the solution of the chemical treatment agent, the solvent used at this time is not particularly limited as long as it can dissolve the chemical treatment agent and does not destroy (e.g., dissolve) the existing carrier structure of the carrier.
Specifically, C may be mentioned 5-12 Alkanes, C 5-12 Cycloalkane, halogenated C 5-12 Alkanes and halogenated C 5-12 Examples of cycloalkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, and chlorocyclohexane, and among these, pentane, hexane, decane, and cyclohexane are preferable, and hexane is most preferable.
These solvents may be used alone or in combination of plural kinds in an arbitrary ratio.
The concentration of the chemical treatment agent in the solution is not particularly limited, and may be appropriately selected as required, as long as it can perform the chemical treatment reaction with a predetermined amount of the chemical treatment agent. As described above, if the chemical treatment agent is in a liquid state, the treatment may be performed directly using the chemical treatment agent, but it may be used after being prepared as a solution of the chemical treatment agent.
In general, the molar concentration of the chemical treatment agent in the solution thereof is generally set to 0.01 to 1.0mol/L, but is not limited thereto.
As a method for performing the chemical treatment, for example, in the case of using a solid chemical treatment agent (such as zirconium tetrachloride), a solution of the chemical treatment agent is first prepared, and then a predetermined amount of the chemical treatment agent is added (preferably dropwise) to the carrier to be treated; in the case of using a liquid chemical treatment agent such as titanium tetrachloride, a predetermined amount of the chemical treatment agent may be directly (but may also be after preparation into a solution) added (preferably dropwise) to the carrier to be treated, and the chemical treatment reaction (with stirring if necessary) may be carried out at a reaction temperature of-30 to 60 ℃ (preferably-20 to 30 ℃) for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours, followed by filtration, washing and drying.
According to the present invention, the filtration, washing and drying may be performed using a conventional method, wherein the washing solvent may be the same solvent as used in dissolving the chemical treatment agent. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times.
According to the invention, as the chemical treatment agent, the amount is such that the molar ratio of the magnesium compound (solid) in terms of Mg element to the chemical treatment agent in terms of group ivb metal (such as Ti element) reaches 1:0.01-1, preferably 1:0.01 to 0.50, more preferably 1:0.10-0.30.
According to a particular embodiment of the present invention, the method for preparing a composite support staged in situ supported non-metallocene catalyst according to the present invention further comprises a step of pre-treating the modified composite support with a co-chemical treatment agent selected from aluminoxane, alkyl aluminum or any combination thereof, prior to treating the modified composite support with the chemical treatment agent (pre-treatment step). Then, the chemical treatment is performed with the chemical treatment agent in exactly the same manner as described above, except that the modified composite carrier is replaced with the pretreated modified composite carrier.
The chemical assistant is specifically described below.
According to the present invention, examples of the auxiliary chemical agent include aluminoxane and aluminum alkyl.
Examples of the aluminoxane include linear aluminoxanes represented by the following general formula (I): (R) (R) Al- (Al (R) -O) n -O-Al (R), and a cyclic aluminoxane represented by the following general formula (II): - (Al (R) -O-) n+2 -。
In the above formula, the radicals R are identical or different (preferably identical) from one another and are each independently selected from C 1 -C 8 Alkyl groups, preferably methyl, ethyl and isobutyl, most preferably methyl; n is any integer in the range of 1-50, preferably any integer in the range of 10-30.
As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferred, and methylaluminoxane and isobutylaluminoxane are further preferred.
These aluminoxanes may be used singly or in combination of plural kinds in any ratio.
Examples of the aluminum alkyl include compounds represented by the following general formula (III):
Al(R) 3 (III)
wherein the radicals R are identical or different (preferably identical) from one another and are each independently selected from C 1 -C 8 Alkyl groups, preferably methyl, ethyl and isobutyl, most preferably methyl.
Specifically, examples of the aluminum alkyl include trimethylaluminum (Al (CH) 3 ) 3 ) Triethylaluminum (Al (CH) 3 CH 2 ) 3 ) Tripropylaluminum (Al (C) 3 H 7 ) 3 ) Triisobutylaluminum (Al)(i-C 4 H 9 ) 3 ) Tri-n-butyl aluminum (Al (C) 4 H 9 ) 3 ) Triisopentylaluminum (Al (i-C) 5 H 11 ) 3 ) Tri-n-pentylaluminum (Al (C) 5 H 11 ) 3 ) Trihexylaluminum (Al (C) 6 H 13 ) 3 ) Triisohexylaluminum (Al (i-C) 6 H 13 ) 3 ) Diethyl methylaluminum (Al (CH) 3 )(CH 3 CH 2 ) 2 ) And dimethylethylaluminum (Al (CH) 3 CH 2 )(CH 3 ) 2 ) Among these, trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable, and triethylaluminum and triisobutylaluminum are most preferable.
These aluminum alkyls may be used alone or in combination of plural kinds in any ratio.
According to the present invention, the auxiliary chemical agent may be the aluminoxane alone or the aluminum alkyl alone, but may be any mixture of the aluminoxane and the aluminum alkyl. The proportions of the components in the mixture are not particularly limited, and may be arbitrarily selected as needed.
According to the invention, the chemical-assisted treatment agent is generally used in the form of a solution. In preparing the solution of the co-chemical treatment agent, the solvent used at this time is not particularly limited as long as it can dissolve the co-chemical treatment agent and does not destroy (e.g., dissolve) the existing carrier structure of the carrier.
Specifically, examples of the solvent include C 5-12 Alkanes and halogenated C 5-12 Examples of alkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane and the like, and among these, pentane, hexane, decane and cyclohexane are preferable, and hexane is most preferable.
These solvents may be used alone or in combination of plural kinds in an arbitrary ratio.
The concentration of the auxiliary chemical treatment agent in the solution is not particularly limited, and may be appropriately selected as required, as long as it can perform the pretreatment with a predetermined amount of the auxiliary chemical treatment agent.
As a method for carrying out the pretreatment, for example, there may be mentioned a method in which a solution of the co-chemical treatment agent is first prepared, then the co-chemical treatment agent solution (containing a predetermined amount of the co-chemical treatment agent) is metered (preferably dropwise) into the carrier to be pretreated with the co-chemical treatment agent at a temperature of-30 to 60 ℃ (preferably-20 to 30 ℃) or the carrier is metered into the co-chemical treatment agent solution, thereby forming a reaction mixture, and the reaction mixture is allowed to react for 1 to 8 hours, preferably 2 to 6 hours, and most preferably 3 to 4 hours (with stirring as necessary). The pretreated product obtained is then isolated from the reaction mixture by filtration, washing (1 to 6 times, preferably 1 to 3 times) and optionally drying, or alternatively, it may be used directly in the form of a mixture without such isolation for the subsequent reaction step (i.e. the aforementioned chemical treatment step). At this time, since a certain amount of solvent is already contained in the mixed solution, the amount of solvent involved in the subsequent reaction step can be reduced accordingly.
According to the present invention, as the co-chemical treatment agent, the amount is used such that the molar ratio of the magnesium compound (solid) in terms of Mg element to the co-chemical treatment agent in terms of Al element is 1:0-1.0, preferably 1:0-0.5, more preferably 1:0.1-0.5.
It is known to those skilled in the art that all of the process steps described above are preferably carried out under substantially anhydrous and oxygen-free conditions. As used herein, substantially anhydrous and oxygen-free means that the water and oxygen content of the system is continuously less than 10ppm. In addition, the composite carrier subsection in-situ supported non-metallocene catalyst of the invention is usually required to be preserved for standby under micro positive pressure under a closed condition after being prepared.
According to the invention, the molar ratio of the magnesium compound to the non-metallocene ligand, calculated as Mg element, is 1:0.0001-1, preferably 1:0.0002 to 0.4, more preferably 1:0.0008 to 0.2, further preferably 1:0.001-0.1, wherein the ratio of the magnesium compound to tetrahydrofuran is 1mol:0.5 to 10L, preferably 1mol:1 to 8L, more preferably 1mol: 2-6L of a mass ratio of the magnesium compound to the porous carrier calculated by the solid magnesium compound is 1:0.1-20, preferably 1:0.5-10, more preferably 1:1-5, wherein the volume ratio of the precipitant to tetrahydrofuran is 1:0.2 to 5, preferably 1:0.5 to 2, more preferably 1:0.8 to 1.5, and the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as group ivb metal element is 1:0.01-1, preferably 1:0.01 to 0.50, more preferably 1:0.10-0.30.
In one embodiment, the present invention also relates to supported non-metallocene catalysts (sometimes also referred to as supported non-metallocene olefin polymerization catalysts) made by the aforementioned method of preparing a composite support staged in situ supported non-metallocene catalyst.
In a further embodiment, the present invention relates to a process for homo/co-polymerizing olefins wherein the olefin is homo-or co-polymerized using the composite support staged in situ supported non-metallocene catalyst of the present invention as catalyst for olefin polymerization.
The olefin homo/copolymerization method according to the present invention is not particularly limited, and other matters (such as a polymerization reactor, an olefin amount, a catalyst, an addition mode of olefin, etc.) which are not explicitly described below may be directly applied to those conventionally known in the art, and the descriptions thereof are omitted here.
According to the homo/copolymerization method of the invention, the composite carrier subsection in-situ supported non-metallocene catalyst of the invention is used as a main catalyst, and one or more selected from aluminoxane, alkyl aluminum, halogenated alkyl aluminum, borane, alkyl boron and alkyl boron ammonium salt are used as cocatalysts to homo or copolymerize olefin.
The main catalyst and the cocatalyst can be added into the polymerization reaction system by adding the main catalyst, then adding the cocatalyst, or adding the cocatalyst, then adding the main catalyst, or adding the main catalyst and the cocatalyst after contact and mixing, or adding the main catalyst and the cocatalyst simultaneously. When the main catalyst and the cocatalyst are added respectively, the main catalyst and the cocatalyst can be added in the same feeding pipeline in sequence or in multiple feeding pipelines in sequence, and when the main catalyst and the cocatalyst are added respectively and simultaneously, multiple feeding pipelines are selected. For continuous polymerization, it is preferable that the multiple feed lines are fed simultaneously and continuously, while for batch polymerization, it is preferable that the two are mixed first and then fed together in the same feed line, or that the cocatalyst is fed first and then the main catalyst is fed in the same feed line.
The reaction mode of the olefin homo/copolymerization process according to the present invention is not particularly limited, and those known in the art can be employed, and examples thereof include a slurry process, an emulsion process, a solution process, a bulk process, and a gas phase process, and among them, a slurry process and a gas phase process are preferable.
According to the present invention, examples of the olefin include C 2 ～C 10 Mono-olefins, di-olefins, cyclic olefins and other ethylenically unsaturated compounds.
Specifically, as the C 2 ～C 10 Examples of the mono-olefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and styrene; examples of the cyclic olefin include 1-cyclopentene and norbornene; examples of the diolefin include 1, 4-butadiene, 2, 5-pentadiene, 1, 6-hexadiene, norbornadiene, and 1, 7-octadiene; examples of the other ethylenically unsaturated compound include vinyl acetate and (meth) acrylate. Among them, homopolymerization of ethylene or copolymerization of ethylene with propylene, 1-butene or 1-hexene is preferable.
According to the invention, homopolymerization refers to the polymerization of only one of said olefins, whereas copolymerization refers to the polymerization between two or more of said olefins.
According to the invention, the cocatalyst is selected from the group consisting of alumoxanes, alkyl aluminums, haloalkylaluminum, boroalkanes, alkyl boron and alkyl boron ammonium salts, of which alumoxanes and alkyl aluminums are preferred.
As the aluminoxane, for example, there may be mentioned a linear aluminoxane represented by the following general formula (I-1) An alkane: (R) (R) Al- (Al (R) -O) n -O-Al (R) (R), and a cyclic aluminoxane represented by the following general formula (II-1): - (Al (R) -O-) n+2 -。
In the above formula, the radicals R are identical or different (preferably identical) from one another and are each independently selected from C 1 -C 8 Alkyl groups, preferably methyl, ethyl and isobutyl, most preferably methyl; n is any integer in the range of 1-50, preferably any integer in the range of 10-30.
As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferred, methylaluminoxane and isobutylaluminoxane are further preferred, and methylaluminoxane is most preferred.
These aluminoxanes may be used singly or in combination of plural kinds in any ratio.
Examples of the aluminum alkyl include compounds represented by the following general formula (III-1):
Al(R) 3 (III-1)
wherein the radicals R are identical or different (preferably identical) from one another and are each independently selected from C 1 -C 8 Alkyl groups, preferably methyl, ethyl and isobutyl, most preferably methyl.
Specifically, examples of the aluminum alkyl include trimethylaluminum (Al (CH) 3 ) 3 ) Triethylaluminum (Al (CH) 3 CH 2 ) 3 ) Tripropylaluminum (Al (C) 3 H 7 ) 3 ) Triisobutylaluminum (Al (i-C) 4 H 9 ) 3 ) Tri-n-butyl aluminum (Al (C) 4 H 9 ) 3 ) Triisopentylaluminum (Al (i-C) 5 H 11 ) 3 ) Tri-n-pentylaluminum (Al (C) 5 H 11 ) 3 ) Trihexylaluminum (Al (C) 6 H 13 ) 3 ) Triisohexylaluminum (Al (i-C) 6 H 13 ) 3 ) Diethyl methylaluminum (Al (CH) 3 )(CH 3 CH 2 ) 2 ) And dimethylethylaluminum (Al (CH) 3 CH 2 )(CH 3 ) 2 ) Among them, trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable, triethylaluminum and triisobutylaluminum are further preferable, and triethylaluminum is most preferable.
These aluminum alkyls may be used alone or in combination of plural kinds in any ratio.
As the haloalkylaluminum, the borane, the alkylboron and the alkylboron ammonium salt, those conventionally used in the art may be directly used without particular limitation.
In addition, according to the present invention, one kind of the above-mentioned cocatalysts may be used alone, or a plurality of kinds of the above-mentioned cocatalysts may be used in combination in an arbitrary ratio as required, without particular limitation.
According to the present invention, depending on the reaction mode of the olefin homo/copolymerization method, a solvent for polymerization may be used.
As the solvent for polymerization, those conventionally used in the art for homo/copolymerization of olefins can be used, and there is no particular limitation.
Examples of the solvent for polymerization include C 4-10 Alkanes (such as butane, pentane, hexane, heptane, octane, nonane, decane, etc.), halogenated C' s 1-10 Alkanes (such as methylene chloride), aromatic hydrocarbon solvents (such as toluene and xylene), ether solvents (such as diethyl ether or tetrahydrofuran), ester solvents (such as ethyl acetate), and ketone solvents (such as acetone), and the like. Among them, hexane is preferably used as the solvent for polymerization.
These polymerization solvents may be used alone or in combination of plural kinds in an arbitrary ratio.
According to the present invention, the polymerization pressure of the olefin homo/copolymerization method is generally 0.1 to 10MPa, preferably 0.1 to 4MPa, more preferably 1 to 3MPa, but is not limited thereto in some cases. According to the present invention, the polymerization temperature is generally-40 to 200 ℃, preferably 10 to 100 ℃, more preferably 40 to 90 ℃, but is not limited thereto in some cases.
In addition, according to the present invention, the olefin homo/copolymerization process may be performed in the presence of hydrogen or in the absence of hydrogen. The partial pressure of hydrogen, when present, may be 0.01% to 99%, preferably 0.01% to 50%, of the polymerization pressure, but is sometimes not limited thereto.
According to the present invention, in carrying out the olefin homo/copolymerization process, the molar ratio of the cocatalyst in terms of aluminum or boron to the composite support staged in situ supported non-metallocene catalyst in terms of group IVB metal is generally 1:1 to 1000, preferably 1:1 to 500, more preferably 1:10 to 500, but is not limited thereto in some cases.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Polymer bulk Density (in g/cm) 3 ) The measurement of (C) is performed by referring to the national standard GB 1636-79.
The content of IVB-group metal (such as Ti) and Mg in the composite carrier segmented in-situ supported non-metallocene catalyst is determined by adopting an ICP-AES method, and the content of the non-metallocene ligand is determined by adopting an elemental analysis method.
The polymerization activity of the catalyst was calculated as follows: after the polymerization reaction is completed, the polymerization product in the reaction vessel is filtered and dried, and then the mass of the polymerization product is weighed, and the polymerization activity of the catalyst (unit is kg polymer/g catalyst or kg polymer/gCat) is expressed as a ratio of the mass of the polymerization product divided by the mass of the composite support segment in-situ supported non-metallocene catalyst used.
The viscosity average molecular weight of the polymer was calculated as follows: the intrinsic viscosity of the polymer was measured according to the standard ASTM D4020-00 using a high temperature dilution Ubbelohde viscometer (capillary inner diameter of 0.44mm, constant temperature bath medium of 300 # silicone oil, solvent for dilution of decalin, measurement temperature of 135 ℃ C.), and then the viscosity average molecular weight Mv of the polymer was calculated according to the following formula.
Mv＝5.37×10 4 ×[η] 1.37
Wherein η is the intrinsic viscosity.
The determination of the tetrahydrofuran content in the composite carrier is carried out according to the following method: quantitative analysis is carried out by capillary gas chromatography, an Agilent 6890N-type gas chromatograph is adopted as an instrument, and an automatic sampler and a hydrogen Flame Ionization Detector (FID) are arranged; the column was DB-1 (30 m. Times.0.32 mm. Times.0.25 μm), gas chromatography operating conditions: temperature: the gasification chamber is 250 ℃, the column temperature is 60 ℃, and the detector is 250 ℃; the carrier gas is high-purity nitrogen; the flow rate of the carrier gas is 1.4ml/min; the split ratio was 70:1, a step of; the sample injection amount is 0.2ml; the reagents for the test were chromatographically pure tetrahydrofuran and ethanol. Relative retention time determined tetrahydrofuran as 2.951min, ethanol as 2.426min, correction factor determined tetrahydrofuran as 3.5182, ethanol as 5.1289. Three solutions of tetrahydrofuran to be detected with different concentrations in reagent ethanol are accurately prepared as standard samples, correction factors of all components are calculated by an area normalization method under the condition of gas chromatography, and a relation diagram of tetrahydrofuran concentration index and actual concentration is prepared. Accurately weighing 2.0g of composite carrier, adding 20ml of ethanol reagent, stirring and dissolving for 30min at normal temperature, filtering, and collecting filtrate for later use. Under the condition of gas chromatography, adding quantitative filtrate into an automatic sampler, automatically performing program sample injection measurement, dividing the area of a tetrahydrofuran peak to be detected by the normalized total area to calculate a filtrate tetrahydrofuran concentration index, substituting the index into a relation diagram to obtain the actual tetrahydrofuran concentration, and finally obtaining the tetrahydrofuran content in the composite carrier after conversion.
Example 1
The magnesium compound adopts anhydrous magnesium chloride, the porous carrier adopts silicon dioxide, namely silica gel, and the model is ES757 of Ineos company. The silica gel was first heat activated by continuous calcination at 600℃under nitrogen atmosphere for 4 hours. The non-metallocene ligand adopts the structural formula asThe precipitant is hexane, and the chemical treating agent is titanium tetrachloride.
2.5g of anhydrous magnesium chloride (MgCl) of magnesium compound was weighed out 2 ) Adding a certain amount of tetrahydrofuran, heating to 60deg.C for dissolving, and stirring at 60deg.CStirring to dissolve completely, adding silica gel to form mixed slurry, stirring for 2 hr, adding precipitant hexane to precipitate, filtering, collecting solid product, and washing with hexane for 2 times, each time with hexane in the same amount as the previous amount.
The obtained solid product was dried at 45℃under vacuum of 5mBar absolute pressure for 12 hours and then at 100℃under vacuum of 5mBar absolute pressure for 8 hours to prepare a composite carrier having a tetrahydrofuran content of 0.29% by weight.
Weighing 25ml of hexane solvent, adding into the composite carrier, adding a hexane solution of a non-metallocene ligand under stirring, reacting for 4 hours at 30 ℃, filtering, washing with hexane for 3 times, and carrying out vacuum drying for 25ml each time to obtain the modified composite carrier.
25ml of hexane solvent was weighed and added to the modified composite carrier, and titanium tetrachloride (TiCl) was added dropwise over 15min with stirring 4 ) The hexane solution of the chemical treating agent is reacted for 4 hours at 30 ℃, filtered, washed with hexane for 3 times, 25ml each time, and finally vacuumized and dried for 12 hours at 25 ℃ under 5mBar to obtain the supported non-metallocene catalyst.
The mixture ratio is as follows: the ratio of the magnesium compound to the tetrahydrofuran is 1mol:4L; the molar ratio of magnesium compound to non-metallocene ligand is 1:0.004; mass ratio of magnesium compound to porous carrier silica gel is 1:2; the volume ratio of the precipitant hexane to tetrahydrofuran is 1:1, a step of; the molar ratio of the magnesium compound to the chemical treating agent titanium tetrachloride to the titanium tetrachloride is 1:0.20.
the catalyst was designated CAT-1.
Example 2
Substantially the same as in example 1, but with the following modifications:
the mixed slurry was dried at a temperature of 30℃and a vacuum of 5mBar under an absolute pressure for 16 hours without using a precipitant, and then dried at a temperature of 90℃and a vacuum of 5mBar under an absolute pressure for 8 hours to prepare a composite carrier, in which the tetrahydrofuran content was 0.25wt%.
The catalyst was designated CAT-2.
Example 3
Substantially the same as in example 1, but with the following modifications:
before the modified composite carrier is treated with the chemical treatment agent, the modified composite carrier is treated with triethylaluminum (Al (C) 2 H 5 ) 3 ) The auxiliary chemical treating agent is used for pretreatment and modification of the composite carrier.
25ml of hexane solvent was measured and added to the modified composite carrier obtained in example 1, and the auxiliary chemical treatment agent triethylaluminum (Al (C) was added dropwise over 15 minutes with stirring 2 H 5 ) 3 ) After stirring and reacting for 1h, filtering, washing with hexane for 2 times, each time 25ml, filtering, washing, vacuumizing and drying to obtain the pretreated modified composite carrier. The resulting pretreated modified support is used in a subsequent chemical treatment step.
Wherein, the mol ratio of the magnesium compound to the auxiliary chemical treating agent is 1:0.35.
the catalyst was designated CAT-3.
Example 4
Substantially the same as in example 3, but with the following modifications:
the auxiliary chemical treating agent is changed into Methylaluminoxane (MAO).
Wherein: the molar ratio of the magnesium compound to the co-chemical treatment agent is 1:0.5.
the catalyst was designated CAT-4.
Example 5
Substantially the same as in example 1, but with the following modifications:
the obtained solid product was dried at 60℃under vacuum of 5mBar under absolute pressure for 12 hours, and then dried at 120℃under vacuum of 5mBar under absolute pressure for 12 hours to obtain a composite carrier in which tetrahydrofuran content was 0.21wt%.
The catalyst was designated CAT-5.
Example 6
Substantially the same as in example 1, but with the following modifications:
the obtained solid product was dried at 40℃under vacuum of 5mBar under absolute pressure for 12 hours, and then dried at 90℃under vacuum of 5mBar under absolute pressure for 6 hours to obtain a composite carrier, wherein the tetrahydrofuran content was 0.40% by weight.
The catalyst was designated CAT-6.
Comparative example A
Substantially the same as in example 1, but with the following modifications:
adding the mixed slurry into precipitator hexane to precipitate, filtering, collecting a solid product, washing for 2 times, wherein the dosage of the precipitator is the same as the previous dosage, uniformly heating the obtained solid product to 130 ℃, and drying for 24 hours under the vacuum of absolute pressure 5mBar to obtain a composite carrier, wherein the tetrahydrofuran content is 0.02wt%.
The catalyst was designated CAT-A.
Comparative example B
Substantially the same as in example 1, but with the following modifications:
the obtained solid product was dried at 30℃under vacuum at an absolute pressure of 5mBar for 12 hours to obtain a composite support having a tetrahydrofuran content of 1.44% by weight.
The catalyst was designated CAT-B.
Example 7
Magnesium compound magnesium ethoxide (Mg (OC) 2 H 5 ) 2 ) The porous carrier adopts montmorillonite, and the montmorillonite is continuously baked for 6 hours at 400 ℃ under nitrogen atmosphere to be thermally activated. The non-metallocene ligand adopts the structural formula as The precipitant is decane, and the chemical treating agent adopts titanium tetrachloride.
5g of magnesium compound magnesium ethoxide (Mg (OC) 2 H 5 ) 2 ) Adding a certain amount of tetrahydrofuran, heating to 60 ℃ for dissolution, continuously stirring at 60 ℃ for complete dissolution, adding montmorillonite to form mixed slurry, stirring for 4 hours, adding a precipitator decane to precipitate, filtering, and washing with decane for 2 times, wherein the decane dosage is the same as the previous dosage.
The obtained solid product was dried at 50℃under vacuum of 10mBar absolute pressure for 12 hours and then at 110℃under vacuum of 10mBar absolute pressure for 8 hours to prepare a composite carrier having a tetrahydrofuran content of 0.28% by weight.
50ml of decane solvent is measured and added into the composite carrier, decane solution of non-metallocene ligand is added under stirring, after reaction for 4 hours at 30 ℃, solid products are filtered and collected, decane is washed for 2 times, 50ml of decane is used each time, and vacuum drying is carried out to obtain the modified composite carrier.
50ml of decane solvent was weighed, added to the modified composite carrier, and titanium tetrachloride (TiCl) was added dropwise over 15min with stirring 4 ) The decane solution of the chemical treating agent is reacted for 4 hours at 30 ℃, filtered, washed for 3 times with 50ml decane, and finally vacuumized and dried for 16 hours at 25 ℃ and 10mBar to obtain the supported non-metallocene catalyst.
The mixture ratio is as follows: the ratio of the magnesium compound to the tetrahydrofuran is 1mol:6L; the molar ratio of magnesium compound to non-metallocene ligand is 1:0.01; the mass ratio of the magnesium compound to the montmorillonite is 1:1, a step of; the volume ratio of the precipitant decane to tetrahydrofuran is 1:1.4; the molar ratio of the magnesium compound to the chemical treating agent titanium tetrachloride to the titanium tetrachloride is 1:0.26.
the catalyst was designated CAT-7.
Comparative example C
Substantially the same as in example 7, but with the following modifications:
the obtained solid product was heated to 125℃uniformly and dried under vacuum at an absolute pressure of 5mBar for 24 hours to obtain a composite carrier having a tetrahydrofuran content of 0.05% by weight.
The catalyst was designated CAT-C.
Comparative example D
Substantially the same as in example 7, but with the following modifications:
the obtained solid product was dried at 20℃under vacuum at an absolute pressure of 10mBar for 1 hour to obtain a composite carrier having a tetrahydrofuran content of 1.53% by weight.
The catalyst was designated CAT-D.
Example 8 (application example)
The composite carrier subsection in-situ supported non-metallocene catalysts CAT-1 to 7 and CAT-A to D are respectively weighed, and ethylene homo-polymerization, co-polymerization and ultra-high molecular weight polyethylene preparation are respectively carried out with a cocatalyst (triethylaluminum, methylaluminoxane or triisobutylaluminum) under the following conditions according to the following method.
The homopolymerization is as follows: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85 ℃, hydrogen partial pressure 0.2MPa, reaction time 2h. Firstly, adding 2.5 liters of hexane into a polymerization autoclave, starting stirring, then adding 20mg of a composite carrier subsection in-situ supported non-metallocene catalyst and cocatalyst mixture, then adding hydrogen to 0.2MPa, and finally continuously introducing ethylene to ensure that the total polymerization pressure is constant at 0.8MPa. And after the reaction is finished, the gas in the kettle is exhausted, the polymer in the kettle is discharged, and the mass is weighed after the drying. The specific cases of the polymerization reaction and the polymerization evaluation results are shown in table 1.
The copolymerization is as follows: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85 ℃, hydrogen partial pressure 0.2MPa, reaction time 2h. Firstly, adding 2.5 liters of hexane into a polymerization autoclave, starting stirring, then adding 20mg of a composite carrier subsection in-situ supported non-metallocene catalyst and cocatalyst mixture, adding 50g of hexene-1 comonomer at one time, adding hydrogen to 0.2MPa, and finally continuously introducing ethylene to ensure that the total polymerization pressure is constant at 0.8MPa. And after the reaction is finished, the gas in the kettle is exhausted, the polymer in the kettle is discharged, and the mass is weighed after the drying. The specific cases of the polymerization reaction and the polymerization evaluation results are shown in table 1.
The preparation of the ultra-high molecular weight polyethylene is polymerized as follows: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.5MPa, polymerization temperature 70℃and reaction time 6h. Firstly, adding 2.5 liters of hexane into a polymerization autoclave, starting stirring, then adding 20mg of a composite carrier segmented in-situ supported non-metallocene catalyst and cocatalyst mixture, wherein the molar ratio of the cocatalyst to the catalyst active metal is 100, and finally continuously introducing ethylene to ensure that the total polymerization pressure is constant at 0.5MPa. And after the reaction is finished, the gas in the kettle is exhausted, the polymer in the kettle is discharged, and the mass is weighed after the drying. The specific cases of the polymerization reaction and the polymerization evaluation results are shown in table 2.
TABLE 1 summary of the effects of the composite Supported segmented in situ non-metallocene catalysts for olefin polymerization
TABLE 2 polymerization effect list of composite support segment in situ supported non-metallocene catalyst for preparing ultra-high molecular weight polyethylene
As is evident from the comparison of the effects obtained by the numbers 1 and 3 in Table 1, the copolymerization effect of the catalyst is remarkable, that is, the copolymerization activity of the catalyst is higher than that of the homopolymerization activity, and the copolymerization reaction can increase the bulk density of the polymer, that is, improve the particle morphology of the polymer.
As can be seen from the comparison of the effects obtained by the numbers 1 and 2 in Table 1, the polymerization performance obtained at the conditions of the molar ratio of the cocatalyst required for the polymerization process to the catalyst active metal of 50 and 100 is equivalent, thereby indicating that the catalyst provided by the present invention requires a smaller amount of cocatalyst for olefin polymerization.
As can be seen from the comparison of the numbers 1, 2, 4, 7-9 and 10-13 in Table 1 and the numbers 1, 2 and 3, 4 in Table 2, the catalyst obtained by controlling the tetrahydrofuran content in the composite carrier in the preparation process of the catalyst of the present invention has better catalytic activity, polymer bulk density and ultra-high molecular weight polyethylene viscosity average molecular weight than the catalyst obtained when the composite carrier is completely dried or the tetrahydrofuran content is higher.
While the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can make appropriate modifications to these embodiments without departing from the technical spirit and scope of the present invention, and it is apparent that these modified embodiments are also included in the scope of the present invention.

Claims (17)

1. A preparation method of a composite carrier segmented in-situ supported non-metallocene catalyst comprises the following steps:
a step of dissolving a magnesium compound in tetrahydrofuran to obtain a magnesium compound solution;
a step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a mixed slurry;
drying the mixed slurry, or adding a precipitant into the mixed slurry and drying the obtained solid product to obtain a composite carrier, wherein the content of tetrahydrofuran in the composite carrier is 0.15-0.50wt%; and
a step of treating the composite carrier with a non-metallocene ligand to obtain a modified composite carrier; and
treating the modified composite carrier with a chemical treatment agent selected from IVB-group metal compounds to obtain the composite carrier segmented in-situ supported non-metallocene catalyst,
the step of obtaining the composite carrier is carried out in the following manner:
drying the mixed slurry for 4-24h under the vacuum of 5-50mBar absolute pressure at the temperature of 35-55 ℃, then drying for 2-12h under the vacuum of 5-50mBar absolute pressure at the temperature of 80-110 ℃ to obtain the composite carrier,
Alternatively, a precipitant is added to the mixed slurry, the obtained solid product is dried under vacuum of 5-50mBar absolute pressure for 4-24 hours at 35-55 ℃ and then dried under vacuum of 5-50mBar absolute pressure for 2-12 hours at 80-110 ℃ to obtain the composite carrier, optionally after washing,
the porous carrier is selected from one or more of clay, mica, silicon dioxide, aluminum oxide, magnesium oxide, silicon aluminum oxide, magnesium aluminum oxide, titanium dioxide and molecular sieve,
the IVB metal compound is selected from TiCl 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、HfCl 4 And HfBr 4 One or more of the following.
2. The method of preparing according to claim 1, further comprising the step of pre-treating the modified composite support with a co-chemical treatment agent selected from the group consisting of alumoxane, aluminum alkyls, or any combination thereof, prior to treating the modified composite support with the chemical treatment agent.
3. The method of preparation according to claim 1 or 2, wherein the porous support is selected from bentonite, diatomaceous earth, silica and montmorillonite.
4. The method according to claim 1, wherein the magnesium compound is selected from one or more of magnesium halide, alkoxymagnesium, alkylmagnesium halide and alkylalkoxymagnesium.
5. The process according to claim 1, wherein the non-metallocene ligand is selected from one or more of the compounds (A-1) to (A-4) and the compounds (B-1) to (B-4) having the following chemical structural formula:
in all of the above chemical formulas,
q is 0 or 1;
d is 0 or 1;
a is selected from oxygen atom, sulfur atom, selenium atom,-NR 23 R 24 、-N(O)R 25 R 26 、/>-PR 28 R 29 、-P(O)R 30 OR 31 Of sulfone, sulfoxide or-Se (O) R 39 Wherein N, O, S, se and P are each an atom for coordination;
e is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, or a cyano group, wherein N, O, S, se and P are each a coordinating atom;
f is selected from nitrogen atom, nitrogen-containing group, oxygen-containing group, sulfur-containing group, selenium-containing group or phosphorus-containing group
A group wherein N, O, S, se and P are each an atom for coordination;
g is selected from C 1 －C 30 Hydrocarbyl, substituted C 1 －C 30 Hydrocarbon or inert functional groups;
y is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, or a phosphorus-containing group, wherein N, O, S, se and P are each an atom for coordination;
z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, or a cyano group, wherein N, O, S, se and P are each a coordinating atom;
-represents a covalent bond or an ionic bond;
R 1 to R 4 、R 6 To R 21 Each independently selected from hydrogen, C 1 －C 30 Hydrocarbyl, substituted C 1 －C 30 Hydrocarbyl or inert functional group, R 22 To R 31 、R 39 Each independently selected from hydrogen, C 1 －C 30 Hydrocarbyl or substituted C 1 －C 30 Hydrocarbyl groups, which may be the same or different from each other, wherein adjacent groups may be bonded to each other to form an aromatic ring;
the inert functional groups are selected from halogen, oxygen-containing groups, and nitrogen-containing groupsA group, a silicon-containing group, a germanium-containing group, a sulfur-containing group, a tin-containing group, C 1 －C 10 Ester groups and nitro groups;
R 5 selected from lone pair electrons on nitrogen, hydrogen, C 1 －C 30 Hydrocarbyl, substituted C 1 －C 30 Hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, selenium-containing groups, or phosphorus-containing groups; when R is 5 R in the case of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group 5 N, O, S, P and Se in (3) may be used as the coordinating atoms;
the substituted C 1 －C 30 The hydrocarbon radical being selected from the group consisting of with one or more halogens or C 1 －C 30 C with alkyl as substituent 1 －C 30 A hydrocarbon group.
6. The process according to claim 5, wherein,
the halogen is selected from F, cl, br or I;
the nitrogen-containing group is selected from-NR 23 R 24 、-T-NR 23 R 24 or-N (O) R 25 R 26 ；
The phosphorus-containing groups are selected from-PR 28 R 29 、-P(O)R 30 R 31 or-P (O) R 32 (OR 33 )；
The oxygen-containing group is selected from the group consisting of hydroxy, -OR 34 and-T-OR 34 ；
The sulfur-containing group is selected from the group consisting of-SR 35 、-T-SR 35 、-S(O)R 36 or-T-SO 2 R 37 ；
The selenium-containing group is selected from the group consisting of-Ser 38 、-T-SeR 38 、-Se(O)R 39 or-T-Se (O) R 39 ；
The radicals T being selected from C 1 －C 30 Hydrocarbyl radicals or radicalsSubstituted C 1 －C 30 A hydrocarbon group;
the R is 32 To R 38 Selected from hydrogen, C 1 －C 30 Hydrocarbyl or substituted C 1 －C 30 A hydrocarbon group;
the C is 1 －C 30 The hydrocarbon radical being selected from C 1 －C 30 Alkyl, C 7 －C 30 Alkylaryl, C 7 －C 30 Aralkyl, C 3 －C 30 Cyclic alkyl, C 2 －C 30 Alkenyl, C 2 －C 30 Alkynyl, C 6 －C 30 Aryl, C 8 －C 30 Condensed ring groups or C 4 －C 30 A heterocyclic group, wherein the heterocyclic group contains 1 to 3 groups selected from nitrogen
Heteroatoms of atoms, oxygen atoms or sulfur atoms;
the silicon-containing group is selected from-SiR 42 R 43 R 44 or-T-SiR 45 ；
The germanium-containing group is selected from-GeR 46 R 47 R 48 or-T-GeR 49 ；
The tin-containing group is selected from-SnR 50 R 51 R 52 、-T-SnR 53 or-T-Sn (O) R 54 ；
The R is 42 To R 54 Each independently selected from hydrogen, the foregoing C 1 －C 30 Hydrocarbyl or substituted C as previously described 1 －C 30 Hydrocarbyl radicals, which may be identical or different from one another, wherein adjacent radicals may be bonded to one another to form a bond or a ring, and
the radicals T are as defined above.
7. The process according to claim 1, wherein the IVB-group metal compound is selected from TiCl 4 And ZrCl 4 One or more of the following.
8. The process according to claim 2, wherein the aluminoxane is one or more selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, and the alkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, trihexylaluminum, triisohexylaluminum, diethylmethylaluminum and dimethylethylaluminum.
9. The process according to claim 1, wherein the molar ratio of said magnesium compound to said non-metallocene ligand, calculated as Mg element, is 1:0.0001-1, wherein the ratio of the magnesium compound to tetrahydrofuran is 1mol: 0.5-10L of a mass ratio of the magnesium compound to the porous carrier calculated by the solid magnesium compound is 1:0.1-20, wherein the volume ratio of the precipitant to tetrahydrofuran is 1:0.2 to 5, and the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as group ivb metal element is 1:0.01-1.
10. The method according to claim 2 or 8, wherein the molar ratio of the magnesium compound in terms of Mg element to the co-chemical treatment agent in terms of Al element is 1:0-1.0.
11. The process according to claim 1, wherein the precipitating agent is one or more selected from the group consisting of alkanes, cycloalkanes, haloalkanes and halocycloalkanes.
12. The process according to claim 1, wherein the magnesium compound is selected from magnesium chloride and/or ethoxymagnesium.
13. The method of claim 1, wherein the non-metallocene ligand is selected from one or more of the compounds having the following chemical formulas:
14. The method according to claim 2, wherein the aluminoxane is one or more selected from the group consisting of methylaluminoxane and isobutylaluminoxane, and the alkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum.
15. The process according to claim 1, wherein the molar ratio of said magnesium compound to said non-metallocene ligand, calculated as Mg element, is 1:0.001-0.1, wherein the ratio of the magnesium compound to tetrahydrofuran is 1mol: 2-6L of a mass ratio of the magnesium compound to the porous carrier calculated by the solid magnesium compound is 1:1-5, wherein the volume ratio of the precipitant to tetrahydrofuran is 1:0.8 to 1.5, and the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as group ivb metal element is 1:0.10-0.30.
16. The method according to claim 2 or 8, wherein the molar ratio of the magnesium compound in terms of Mg element to the co-chemical treatment agent in terms of Al element is 1:0.1-0.5.
17. The process according to claim 1, wherein the precipitant is one or more selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, chlorobutane, chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane and bromocyclodecane.
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WO1999035173A1 (en) * 1997-12-31 1999-07-15 Elenac Gmbh Catalyst for producing ethylene homopolymers and copolymers
EP2202246A1 (en) * 2007-10-16 2010-06-30 Sinopec Yangzi Petrochemical Company Ltd. Non-metallocene catalyst supported on magnesium compound and its preparation method
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Patent Citations (3)

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WO1999035173A1 (en) * 1997-12-31 1999-07-15 Elenac Gmbh Catalyst for producing ethylene homopolymers and copolymers
EP2202246A1 (en) * 2007-10-16 2010-06-30 Sinopec Yangzi Petrochemical Company Ltd. Non-metallocene catalyst supported on magnesium compound and its preparation method
CN102964479A (en) * 2011-08-31 2013-03-13 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application

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