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CN110964138A - Magnesium single-carrier segmented in-situ supported non-metallocene catalyst and preparation method thereof - Google Patents

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

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CN110964138A
CN110964138A CN201910019293.0A CN201910019293A CN110964138A CN 110964138 A CN110964138 A CN 110964138A CN 201910019293 A CN201910019293 A CN 201910019293A CN 110964138 A CN110964138 A CN 110964138A
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magnesium
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CN110964138B (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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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/645—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643
    • C08F4/6452—Component of C08F4/64 containing at least two different metals
    • C08F4/6455—Component of C08F4/64 containing at least two different metals containing magnesium
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a magnesium single-carrier segmented in-situ supported non-metallocene catalyst, a preparation method and application thereof. The preparation method of the magnesium single-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; drying the magnesium compound solution, or adding a precipitant into the magnesium compound solution and drying the obtained solid product to obtain a magnesium carrier, wherein the tetrahydrofuran content in the magnesium carrier is 0.10-0.50 wt%; treating the magnesium carrier with a non-metallocene ligand to obtain a modified carrier; and treating the modified carrier with a chemical treatment agent selected from IVB group metal compounds to obtain the magnesium single carrier segmented in-situ supported non-metallocene catalyst. The magnesium single-carrier segmented in-situ supported non-metallocene catalyst has the characteristics of simple and feasible preparation method, flexible and adjustable polymerization activity and the like.

Description

Magnesium single-carrier segmented in-situ supported non-metallocene catalyst and preparation method thereof
Technical Field
The invention relates to a non-metallocene catalyst. Specifically, the invention relates to a magnesium single-carrier segmented in-situ supported non-metallocene catalyst, a preparation method thereof and application thereof in olefin homopolymerization/copolymerization.
Background
Non-metallocene catalyst appearing in the middle and later 90 s of the 20 th century is also called as post-metallocene catalyst, the central atom of the main catalyst comprises almost all transition metal elements, the structure does not contain cyclopentadiene (metallocene) and derivative groups thereof (indene or fluorene and the like), and the coordination atom is oxygen, nitrogen, sulfur, phosphorus and the like, and the catalyst is characterized in that the central ion has stronger electrophilicity, has a cis-alkyl or halogen metal central structure, is easy to insert olefin and transfer sigma-bond, is easy to alkylate the central metal, and is beneficial to the generation of a cation active center; the formed complex has a limited geometrical configuration, stereoselectivity, electronegativity and chiral adjustability. In addition, the metal-carbon bonds formed are readily polarized, facilitating the polymerization of olefins. Therefore, a higher molecular weight olefin polymer can be obtained even at a higher polymerization temperature.
However, homogeneous olefin polymerization catalysts have been proved to have the disadvantages of short duration of activity, low utilization rate of active centers (easy bimolecular deactivation), easy sticking of the produced polymer to the kettle, high aluminoxane dosage (high preparation cost) in the polymerization process, and only being applicable to solution polymerization process, thus severely limiting the industrial application thereof.
The catalyst or the catalyst system prepared by patent documents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 has wide olefin homopolymerization/copolymerization performance and is suitable for various polymerization processes, but the catalyst or the catalyst system disclosed by the patent documents needs higher cocatalyst dosage during olefin polymerization to obtain proper olefin polymerization activity, and a kettle sticking phenomenon exists in the polymerization process.
In order to overcome the disadvantages of the homogeneous catalyst system, a general method is to load a homogeneous catalyst such as a non-metallocene catalyst on a carrier to prepare a supported catalyst, thereby improving the polymerization performance of olefins and the particle morphology of the obtained polymer, and enabling the supported catalyst to meet more polymerization processes, such as gas phase polymerization or slurry polymerization.
For the non-metallocene catalysts disclosed in patent documents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207, patent documents CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501, 200510119401.x, etc. are supported in various ways to obtain supported non-metallocene catalysts, but these patent documents all involve supporting a non-metallocene organic compound containing a transition metal (or referred to as a non-metallocene catalyst or a non-metallocene complex) on a treated carrier, or the non-metallocene catalyst has a lower supporting amount, or the non-metallocene catalyst is not tightly bound to the carrier.
Patent document CN200510080210.7 discloses an in-situ synthesized supported vanadium non-metallocene polyolefin catalyst, and a preparation method and application thereof, wherein dialkyl magnesium reacts with acyl naphthol or β -diketone to form acyl naphthol magnesium or β -diketone magnesium compound, and then reacts with chloride of tetravalent vanadium to form a carrier and an active catalytic component at the same time.
Patent document CN200610026765.8 discloses a class of single-site ziegler-natta olefin polymerization catalysts. The catalyst takes salicylaldehyde or substituted salicylaldehyde derivatives containing coordination groups as electron donors, and is obtained by adding a pretreated carrier (such as silica gel), a metal compound (such as titanium tetrachloride) and the electron donors into a magnesium compound (such as magnesium chloride)/tetrahydrofuran solution and treating the carrier and the electron donors.
Patent document CN200610026766.2 discloses a class of organic compounds containing heteroatoms and their use in ziegler-natta catalysts.
Patent document CN200710162676.0 discloses a magnesium compound supported non-metallocene catalyst and a preparation method thereof, 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 of the catalytically active metal and the magnesium compound means that the group IVB metal compound is added into the formed magnesium compound solid (such as the magnesium compound solid or the modified magnesium compound solid), the contact cannot achieve the sufficient reaction of the catalytically active metal and the magnesium compound, and the obtained magnesium compound carrier containing the catalytically active metal is necessarily heterogeneous, not the sufficient contact and reaction among molecules, thereby limiting the function of the non-metallocene ligand added subsequently to be fully exerted.
Similarly, patent document CN200710162667.1 discloses a magnesium compound supported non-metallocene catalyst and its preparation method, which also have similar problems. The catalyst is obtained by directly contacting a compound of a catalytic active metal with a magnesium compound containing a non-metallocene ligand by an in-situ supporting method. However, the contact refers to adding the non-metallocene ligand solution into the formed magnesium compound solid (such as the magnesium compound solid or the modified magnesium compound solid), and the contact cannot achieve the full reaction of the non-metallocene ligand and the magnesium compound, and the obtained magnesium compound carrier containing the non-metallocene ligand is necessarily heterogeneous, not the full contact and reaction among molecules, thereby limiting the full play of the function of the non-metallocene ligand.
Patent document CN200910210990.0 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 in the presence of an alcohol to obtain a magnesium compound solution; adding a precipitant to the magnesium compound solution to obtain a modified carrier; and a step of treating the modified support with a chemical treatment agent selected from group IVB metal compounds to obtain the supported non-metallocene catalyst. It can be seen from the disclosure that the introduced alcohol only acts as a co-solvent for the magnesium compound and the non-metallocene ligand and is then dried off during the drying process.
The problem commonly existed in the prior art of the supported non-metallocene catalyst is that the olefin polymerization activity is low, and in order to improve the activity, the higher using amount of the cocatalyst is needed to be assisted. Further, in the prior art, since silica gel or the like is used as a carrier, the ash content in the polymer obtained by polymerization is high, thereby limiting the practical use of the polymer. The catalyst supported by magnesium compound has heterogeneous composition and distribution, so that the activity of the catalyst is greatly improved.
Therefore, there is still a need for a supported non-metallocene catalyst, which is simple in preparation method, suitable for industrial production, and can overcome the problems of the supported non-metallocene catalyst in the prior art.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art and found that the aforementioned problems can be solved by using a specific preparation method to produce a supported non-metallocene catalyst, particularly by controlling the concentration of tetrahydrofuran as a solvent in a magnesium support to exert its effect in improving the catalyst activity, the polymer particle morphology, and the like, and thus completed the present invention.
In the process for the preparation of the supported non-metallocene catalyst of the present invention, no proton donor (such as those conventionally used in the art) is added. In addition, in the preparation method of the supported non-metallocene catalyst of the present invention, an electron donor (generally known in the art and conventionally used electron donors include compounds such as monoesters, diesters, diethers, diketones and glycol esters) is not added. Furthermore, in the preparation method of the supported non-metallocene catalyst, rigorous reaction requirements and reaction conditions are not required. Therefore, the preparation method of the magnesium single-carrier segmented in-situ supported non-metallocene catalyst is simple and is very suitable for industrial production.
Specifically, the invention relates to a preparation method of a magnesium single-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 drying the magnesium compound solution, or adding a precipitant to the magnesium compound solution and drying the obtained solid product to obtain a magnesium carrier, wherein the tetrahydrofuran content in the magnesium carrier is 0.10 to 0.50 wt%, preferably 0.10 to 0.35 wt%, more preferably 0.11 to 0.25 wt%;
treating the magnesium carrier with a non-metallocene ligand to obtain a modified carrier; and
and treating the modified carrier with a chemical treatment agent selected from IVB group metal compounds to obtain the magnesium single carrier segmented in-situ supported non-metallocene catalyst.
The invention also relates to a magnesium single-carrier segmented in-situ supported non-metallocene catalyst prepared by the preparation method and application thereof in olefin homopolymerization/copolymerization.
Technical effects
With the catalyst preparation method provided by the present invention, it was surprisingly found that by strictly controlling and maintaining a certain tetrahydrofuran content in the magnesium support prepared after the drying step, the catalytic activity and the bulk density of the polymer are significantly improved, and the amount of the cocatalyst required in the polymerization process is also lower.
The magnesium single-carrier segmented in-situ supported non-metallocene catalyst prepared by the method has an obvious copolymerization effect, namely the copolymerization activity of the catalyst is higher than that of homopolymerization, and the copolymerization reaction can improve the bulk density of a polymer, namely the particle form of the polymer.
The magnesium single-carrier segmented in-situ supported non-metallocene catalyst provided by the invention can be used for polymerizing to obtain ultrahigh molecular weight polyethylene with higher molecular weight under the condition of homopolymerization without hydrogen participation.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
In the context of the present invention, unless otherwise explicitly defined, or the meaning is beyond the understanding of those skilled in the art, a hydrocarbon or hydrocarbon derivative group of 3 or more carbon atoms (e.g., propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) has the same meaning when not headed "plus" as when headed "plus". For example, propyl is generally understood to be n-propyl, and butyl is generally understood to be n-butyl.
In the context of the present invention, physical property values (such as boiling point) of a substance are measured at normal temperature (25 ℃) and normal pressure (101325Pa), unless otherwise specifically noted.
The invention relates to a preparation method of a magnesium single-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; drying the magnesium compound solution, or adding a precipitant into the magnesium compound solution and drying the obtained solid product to obtain a magnesium carrier, wherein the tetrahydrofuran content in the magnesium carrier is 0.01-0.50 wt%; treating the magnesium carrier with a non-metallocene ligand to obtain a modified carrier; and treating the modified carrier with a chemical treatment agent selected from IVB group metal compounds to obtain the magnesium single 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 1 mol: 0.5-10L, preferably 1 mol: 1 to 8L, more preferably 1 mol: 2-6L.
According to the present 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 facilitate the dissolution of the magnesium compound. The stirring can be in any form, such as a stirring paddle (the rotating speed is generally 10-1000 rpm), and the like. If necessary, the dissolution may be promoted by appropriate heating.
The magnesium compound will be specifically described below.
According to the present invention, the term "magnesium compound" is used in a general concept in the art to refer to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a support for supported olefin polymerization catalysts.
According to the present invention, examples of the magnesium compound include magnesium halide, alkoxy magnesium, alkyl magnesium halide and alkyl alkoxy magnesium.
Specifically, the magnesium halide includes, for example, magnesium chloride (MgCl)2) Magnesium bromide (MgBr)2) Magnesium iodide (MgI)2) And magnesium fluoride (MgF)2) And the like, among which magnesium chloride is preferred.
Examples of the alkoxymagnesium halide include methoxymagnesium chloride (Mg (OCH)3) Cl), magnesium ethoxychloride (Mg (OC)2H5) Cl), propoxymagnesium chloride (Mg (OC)3H7) Cl), n-butoxy magnesium chloride (Mg (OC)4H9) Cl), isobutoxy magnesium chloride (Mg (i-OC)4H9) Cl), methoxy magnesium bromide (Mg (OCH)3) Br), magnesium ethoxybromide (Mg (OC)2H5) Br), propoxymagnesium bromide (Mg (OC)3H7) Br), n-butoxy magnesium bromide (Mg (OC)4H9) Br), isobutoxy magnesium bromide (Mg: (i-OC4H9) Br), methoxy magnesium iodide (Mg (OCH)3) I), magnesium ethoxyiodide (Mg (OC)2H5) I), propoxyatomagnesium iodide (Mg (OC)3H7) I), magnesium n-butoxide iodide (Mg (OC)4H9) I) and isobutoxy magnesium iodide (Mg (I-OC)4H9) I) and the like, among 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)2H5)2) Magnesium propoxide (Mg (OC)3H7)2) Magnesium butoxide (Mg (OC)4H9)2) Isobutoxy magnesium (Mg (i-OC)4H9)2) And 2-ethylhexyloxymagnesium (Mg (OCH)2CH(C2H5)C4H-)2) And the like, among which magnesium ethoxide and magnesium isobutoxide are preferable.
Examples of the alkyl magnesium include methyl magnesium (Mg (CH)3)2) Ethyl magnesium (Mg (C)2H5)2) Propyl magnesium (Mg (C)3H7)2) N-butylmagnesium (Mg (C)4H9)2) And isobutyl magnesium (Mg (i-C)4H9)2) Etc., among which ethyl magnesium and n-butyl magnesium are preferred.
Examples of the alkyl magnesium halide include methyl magnesium chloride (Mg (CH)3) Cl), ethylmagnesium chloride (Mg (C)2H5) Cl), propylmagnesium chloride (Mg (C)3H7) Cl), n-butylmagnesium chloride (Mg (C)4H9) Cl), isobutyl magnesium chloride (Mg (i-C)4H9) Cl), methyl magnesium bromide (Mg (CH)3) Br), ethyl magnesium bromide (Mg (C)2H5) Br), propyl magnesium bromide (Mg (C)3H7) Br), n-butylmagnesium bromide (Mg (C)4H9) Br), isobutyl magnesium bromide (Mg (i-C)4H9) Br), methyl magnesium iodide (Mg (CH)3) I), ethyl magnesium iodide (Mg (C)2H5) I), propylmagnesium iodide (Mg (C)3H7) I), n-butyl magnesium iodide (Mg (C)4H9) I) and isobutyl magnesium iodide (Mg (I-C)4H9) I) and the like, wherein methyl magnesium chloride, ethyl magnesium chloride and isobutyl magnesium chloride are preferred.
Examples of the magnesium alkylalkoxy include methyloxymagnesium (Mg (OCH)3)(CH3) Methyl magnesium ethoxide (Mg (OC)2H5)(CH3) Methyl propoxy magnesium (Mg (OC)3H7)(CH3) Methyl n-butoxy magnesium (Mg (OC)4H9)(CH3) Methyl isobutoxy magnesium (Mg (i-OC)4H9)(CH3) Ethyl methoxy magnesium (Mg (OCH)3)(C2H5) Ethyl magnesium ethoxide (Mg (OC)2H5)(C2H5) Ethyl propoxy magnesium (Mg (OC)3H7)(C2H5) Ethyl n-butoxy magnesium (Mg (OC)4H9)(C2H5) Ethyl isobutoxy magnesium (Mg (i-OC)4H9)(C2H5) Propyl methoxy magnesium (Mg (OCH)3)(C3H7) Propylmagnesium ethoxide (Mg (OC)2H5)(C3H7) Propylmagnesium propoxide (Mg (OC)3H7)(C3H7) Propyl n-butoxy magnesium (Mg (OC)4H9)(C3H7) Propyl iso-butoxy magnesium (Mg (i-OC)4H9)(C3H7) N-butyl methoxy magnesium (Mg (OCH)3)(C4H9) N-butyl ethoxy magnesium (Mg (OC)2H5)(C4H9) N-butyl propoxy magnesium (Mg (OC)3H7)(C4H9) N-butyl n-butoxy magnesium (Mg (OC)4H9)(C4H9) N-butyl isobutoxy magnesium (Mg (i-OC)4H9)(C4H9) Isobutyl methoxy magnesium (Mg (OCH)3)(i-C4H9) Isobutyl ethoxy magnesium (Mg (OC)2H5)(i-C4H9) Isobutyl propoxy magnesium (Mg (OC)3H7)(i-C4H9) Isobutyl n-butoxy magnesium (Mg (OC)4H9)(i-C4H9) Isobutyl isobutoxy magnesium (Mg (i-OC)4H9)(i-C4H9) Etc.), among which butyl magnesium ethoxide is preferred.
These magnesium compounds may be used alone or in combination of two or more, 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.
drying the magnesium compound solution, or adding a precipitant to the magnesium compound solution to precipitate a solid substance from the magnesium compound solution and drying the resulting solid product to obtain the magnesium carrier.
The precipitant is specifically described below.
According to the present invention, the term "precipitating agent" is used in the usual sense of the art and refers to a chemically inert liquid capable of reducing the solubility of a solute (such as the magnesium compound) in its solution and thereby causing it to precipitate out of the solution as a solid.
According to the present invention, examples of the precipitant include a poor solvent for the magnesium compound and a good solvent for tetrahydrofuran for dissolving the magnesium compound, such as an alkane, a cycloalkane, a haloalkane, and a haloalkylcycloalkane.
Examples of the alkane include pentane, hexane, heptane, octane, nonane, decane, etc., 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 dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, and tribromobutane.
Examples of the halogenated cycloalkane include chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane.
These precipitants may be used singly or in combination of two or more at an arbitrary ratio.
The addition mode of the precipitant can be one-time addition or dropwise addition, and preferably one-time addition. During this precipitation, stirring may be used to facilitate dispersion of the precipitant in the magnesium compound solution and to facilitate final precipitation of the solid product. The stirring can be in any form, such as a stirring paddle (the rotating speed is generally 10-1000 rpm), and the like.
The amount of the precipitant to be used 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 precipitant is not particularly limited, but is preferably ordinary temperature. Moreover, the precipitation process is also preferably carried out at normal temperature in general.
After complete precipitation, the solid product obtained is filtered, optionally washed and dried to obtain the magnesium support. The method of filtration and washing is not particularly limited, and those conventionally used in the art may be used as needed.
The washing is generally carried out 1 to 6 times, preferably 2 to 3 times, as required. Among them, the washing solvent is preferably the same as the precipitant, but may be different.
The method of drying is not particularly limited as long as the tetrahydrofuran content in the magnesium carrier is controlled to be in the range of 0.10 to 0.50 wt%, preferably 0.10 to 0.35 wt%, more preferably 0.11 to 0.25 wt% by drying the magnesium compound solution or by drying the solid product (optionally after washing).
According to the present invention, the drying can 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 manner (including drying temperature, drying vacuum degree and drying time) is limited by the condition that the tetrahydrofuran content of the magnesium carrier meets the requirements of the invention. For example, the magnesium compound solution is dried at a temperature of 15 to 60 ℃, preferably 35 to 55 ℃, under a vacuum of 2 to 100mBar absolute pressure, preferably 5 to 50mBar, for 2 to 30h, preferably 4 to 12h, and then dried at a temperature of 65 to 100 ℃, preferably 70 to 90 ℃, under a vacuum of 2 to 100mBar absolute pressure, preferably 5 to 50mBar, for 1 to 20h, preferably 2 to 8h, thereby obtaining the magnesium support. Alternatively, a precipitant is added to the magnesium compound solution and the solid product obtained (optionally after washing) is dried at a temperature of 15-60 ℃, preferably 35-55 ℃ under a vacuum of 2-100mBar absolute pressure, preferably 5-50mBar, for 2-30h, preferably 4-12h, and then at a temperature of 65-100 ℃, preferably 70-90 ℃ under a vacuum of 2-100mBar absolute pressure, preferably 5-50mBar, for 1-20h, preferably 2-8h, whereby the magnesium support is obtained.
According to the invention, the magnesium support is treated with a non-metallocene ligand to obtain a modified support.
According to the present invention, the term "non-metallocene complex" is a single-site olefin polymerization catalyst relative to a metallocene catalyst, a metallo-organic compound which does not contain a cyclopentadienyl group such as a metallocene ring, a fluorene ring or an indene ring or a derivative thereof in the structure and is capable of exhibiting an 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 polydentate ligand (preferably a tridentate or more) coordinately bound to said central metal atom, whereas the term "non-metallocene ligand" is the aforementioned polydentate ligand.
According to the invention, the non-metallocene ligand is selected from compounds having the following chemical structural formula:
Figure BDA0001940198150000091
according to the present invention, the groups A, D and E (coordinating groups) in the compound form a coordination bond by coordination reaction of the coordinating atoms (e.g., heteroatoms such as N, O, S, Se and P) contained therein with the group IVB metal atom contained in the group IVB metal compound used as the chemical treatment 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 compound (a) and compound (B) having the following chemical structural formula:
Figure BDA0001940198150000101
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:
Figure BDA0001940198150000102
Figure BDA0001940198150000111
in all of the above chemical structural formulae,
q is 0 or 1;
d is 0 or 1;
a is selected from oxygen atom, sulfur atom, selenium atom,
Figure BDA0001940198150000112
-NR23R24、-N(O)R25R26、
Figure BDA0001940198150000113
-PR28R29、-P(O)R30OR31Sulfone group, sulfoxide group or-Se (O) R39Wherein N, O, S, Se and P are each coordinating atoms;
b is selected from nitrogen atom, nitrogen-containing group, phosphorus-containing group or C1－C30A hydrocarbyl group;
d is selected from nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing group, C1－C30A 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 C1－C30Hydrocarbyl, substituted C1－C30A hydrocarbyl or inert functional group;
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 a coordinating atom;
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 (-CN), and examples thereof include-NR23R24、-N(O)R25R26、-PR28R29、-P(O)R30R31、-OR34、-SR35、-S(O)R36、-SeR38or-Se (O) R39Wherein N, O, S, Se and P are each coordinating atoms;
→ represents a single bond or a double bond;
-represents a covalent or ionic bond.
R1To R4、R6To R21Each independently selected from hydrogen,C1－C30Hydrocarbyl, substituted C1－C30Hydrocarbyl (of which halogenated hydrocarbyl is preferred, such as-CH)2Cl and-CH2CH2Cl) or inert functional groups. R22To R36、R38And R39Each independently selected from hydrogen and C1－C30Hydrocarbyl or substituted C1－C30Hydrocarbyl (of which halogenated hydrocarbyl is preferred, such as-CH)2Cl and-CH2CH2Cl). The above groups may be the same or different from each other, wherein adjacent groups such as R1And R2，R6And R7，R7And R8，R8And R9，R13And R14，R14And R15，R15And R16，R18And R19，R19And R20，R20And R21，R23And R24Or R is25And R26Etc. 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 substituted aromatic ring having 1 to 4 carbon atoms1－C30Hydrocarbyl or substituted C1－C30Hydrocarbyl (of which halogenated hydrocarbyl is preferred, such as-CH)2Cl and-CH2CH2Cl) substituted benzene ring.
R5Selected from lone pair of electrons on nitrogen, hydrogen, C1－C30Hydrocarbyl, substituted C1－C30A hydrocarbyl group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group. When R is5When it is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R5N, O, S, P and Se in (1) can be used as a coordinating atom (coordinating with the central metal atom M).
In the context of the present invention, examples of said inert functional groups are selected from the group consisting of halogens, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C1－C10Ester group or nitro group (-NO)2) And (C) and the like, but generally does not include C1－C30Alkyl radicals and radicals ofSubstituted C1－C30A hydrocarbyl group.
In the context of the present invention, the inert functional group has the following characteristics, limited by the chemical structure of the polydentate ligand according to the invention:
(1) does not interfere with the process of coordination of the group A, D, E, F, Y or Z to 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 existing coordination of these groups to the central metal atom M.
According to the invention, in all the chemical formulae mentioned above, any two or more radicals adjacent to one another, such as R, are optionally present21With the group Z, or R13Together with the group Y, may be joined to each other to form a ring, preferably forming C containing a heteroatom from said group Z or Y6－C30Aromatic heterocyclic ring, such as pyridine ring, etc., wherein said aromatic heterocyclic ring is optionally substituted with 1 or more selected from C1－C30Hydrocarbyl and substituted C1－C30Substituent of hydrocarbyl.
In the context of the present invention it is,
the halogen is selected from F, Cl, Br or I. The nitrogen-containing group is selected from
Figure BDA0001940198150000131
-NR23R24、-T-NR23R24or-N (O) R25R26. The phosphorus-containing group is selected from
Figure BDA0001940198150000132
-PR28R29、-P(O)R30R31or-P (O) R32(OR33). The oxygen-containing group is selected from hydroxyl, -OR34and-T-OR34. The sulfur-containing group is selected from-SR35、-T-SR35、-S(O)R36or-T-SO2R37. The selenium-containing group is selected from-SeR38、-T-SeR38、-Se(O)R39or-T-Se (O) R39. The group T is selected from C1－C30Hydrocarbyl or substituted C1－C30A hydrocarbyl group. The R is37Selected from hydrogen, C1－C30Hydrocarbyl or substituted C1－C30A hydrocarbyl group.
In the context of the present invention, said C1－C30The hydrocarbon radical being selected from C1－C30Alkyl (preferably C)1－C6Alkyl, e.g. isobutyl), C7－C30Alkaryl (e.g., tolyl, xylyl, diisobutylphenyl, etc.), C7－C30Aralkyl (e.g. benzyl), C3－C30Cyclic alkyl, C2－C30Alkenyl radical, C2－C30Alkynyl, C6－C30Aryl (e.g. phenyl, naphthyl, anthracyl, etc.), C8－C30Condensed ring radicals or C4－C30A heterocyclic group, wherein the heterocyclic group contains 1 to 3 hetero atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom, such as a pyridyl group, a pyrrolyl group, a furyl group, a thienyl group or the like.
According to the invention, in the context of the present invention, said C is defined as being specific to the relevant group to which it is bound1－C30Hydrocarbyl radicals are sometimes referred to as C1－C30Hydrocarbon diyl (divalent radical, otherwise known as C)1－C30Alkylene) or C1－C30Hydrocarbon triyl (trivalent radical), as will be apparent to those skilled in the art.
In the context of the present invention, said substituted C1－C30By hydrocarbyl is meant C bearing one or more inert substituents1－C30A hydrocarbyl group. By inert substituents, it is meant that these substituents are in registry with the aforementioned coordinating groups (meaning the aforementioned groups A, D, E, F, Y and Z, or optionally also R5) The coordination process with the central metal atom M (i.e., the aforementioned group IVB metal atom) is not substantially interfered with; in other words, these substituents have no ability or opportunity (e.g., by steric hindrance, etc.) to interact with the group IVB metal atom, as limited by the chemical structure of the ligands of the present inventionCoordinate reaction to form a coordinate bond. In general, the inert substituent is selected from halogen or C1－C30Alkyl (preferably C)1－C6Alkyl groups such as isobutyl).
In the context of the present invention, the silicon-containing group is selected from the group consisting of-SiR42R43R44or-T-SiR45(ii) a The germanium-containing group is selected from-GeR46R47R48or-T-GeR49(ii) a The tin-containing group is selected from-SnR50R51R52、-T-SnR53or-T-Sn (O) R54(ii) a And said R is42To R54Each independently selected from hydrogen, C1－C30Hydrocarbyl or substituted C of the foregoing1－C30The hydrocarbon group may be the same or different from each other, and adjacent groups may be bonded to each other to form a bond or form a ring. Wherein the group T is as defined above.
Examples of the non-metallocene ligand include the following compounds:
Figure BDA0001940198150000141
Figure BDA0001940198150000151
Figure BDA0001940198150000161
Figure BDA0001940198150000171
the non-metallocene ligand is preferably selected from the following compounds:
Figure BDA0001940198150000172
Figure BDA0001940198150000181
the non-metallocene ligand is further preferably selected from the following compounds:
Figure BDA0001940198150000182
more preferably, the non-metallocene ligand is selected from the following compounds:
Figure BDA0001940198150000191
these non-metallocene ligands may be used singly or in combination in any ratio.
According to the present invention, the non-metallocene ligand is not a diether compound generally 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 the details of the manufacturing method, see, for example, WO03/010207 and chinese patents ZL01126323.7 and ZL02110844.7, etc., which are incorporated herein by reference in their entirety.
According to the invention, the non-metallocene ligand is used, if necessary, in the form of a solution for metering and handling convenience.
In preparing the solution of the non-metallocene ligand, the solvent used in this case is not particularly limited as long as the non-metallocene ligand can be dissolved without destroying (e.g., dissolving) the existing support structure of the support. The solvent includes, for example, C6-12Aromatic hydrocarbons, halogenated C6-12Aromatic hydrocarbon, C5-12Alkanes, halogen radicals C1-10One 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, dichloromethane, dichloroethane, ethyl acetate, and tetrahydrofuran. Among them, C is preferable6-12Aromatic hydrocarbon, C5-12Alkanes, tetrahydrofuran and dichloromethane.
These solvents may be used singly or in combination in any ratio.
When dissolving the non-metallocene ligand, stirring may be used as needed (the rotation speed of the stirring is generally 10 to 500 rpm).
According to the present invention, the ratio 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 the method for carrying out the treatment with the non-metallocene ligand, for example, a solution of the non-metallocene ligand is prepared first, and then the solution (containing a predetermined amount of the non-metallocene ligand) is metered (preferably, dropwise) into the support to be treated at a temperature of-30 to 60 ℃ (preferably, -20 to 30 ℃), or the support is metered into the solution, and the treatment reaction (with stirring if necessary) 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, and then filtration, optional washing and drying are carried out.
According to the present invention, the filtration, washing and drying may be carried out by a conventional method, wherein the solvent for washing may be the same solvent as that used for dissolving the non-metallocene ligand. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, and 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: 0.0002-0.4, more preferably 1: 0.0008 to 0.2, more preferably 1: 0.001-0.1.
Next, the modified support is treated with a chemical treatment agent selected from group ivb metal compounds, thereby obtaining the supported non-metallocene catalyst of the present invention.
According to the invention, the chemical treatment agent can react with the non-metallocene ligand contained in the modified carrier by chemically treating the modified carrier with the chemical treatment agent, so that a non-metallocene complex is generated in situ on the carrier (in-situ supporting reaction), and the supported non-metallocene catalyst is obtained.
The chemical treatment agent is specifically described below.
According to the present invention, a group IVB metal compound is used as the chemical treatment agent.
As the group IVB metal compound, there may be mentioned, for example, a group IVB metal halide, a group IVB metal alkyl compound, a group IVB metal alkoxide, a group IVB metal alkyl halide and a group IVB metal alkoxy halide.
As the group IVB metal halide, the group IVB metal alkyl compound, the group IVB metal alkoxide, the group IVB metal alkyl halide and the group IVB metal alkoxide, for example, a compound having a structure of the following general formula (IV):
M(OR1)mXnR2 4-m－n(IV)
wherein:
m is 0, 1, 2, 3 or 4;
n is 0, 1, 2, 3 or 4;
m is a metal of group IVB of the periodic Table of the elements, such as titanium, zirconium, hafnium, etc.;
x is halogen such as F, Cl, Br, I, etc.; and is
R1And R2Each independently selected from C1-10Alkyl radicals, such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R1And R2May be the same or different.
Specifically, the group IVB metal halide includes, for example, 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 tetramethyltitanium (Ti (CH)3)4) Tetraethyl titanium (Ti (CH)3CH2)4) Tetraisobutyltitanium (Ti (i-C)4H9)4) Tetra-n-butyltitanium (Ti (C)4H9)4) Triethylmethyltitanium (Ti (CH)3)(CH3CH2)3) Diethyl dimethyl titanium (Ti (CH)3)2(CH3CH2)2) Trimethylethyltitanium (Ti (CH)3)3(CH3CH2) Triisobutylmethyltitanium (Ti (CH))3)(i-C4H9)3) Diisobutyldimethyltitanium (Ti (CH)3)2(i-C4H9)2) Trimethylisobutyltitanium (Ti (CH)3)3(i-C4H9) Triisobutylethyltitanium (Ti (CH))3CH2)(i-C4H9)3) Diisobutyl diethyl titanium (Ti (CH)3CH2)2(i-C4H9)2) Triethylisobutyltitanium (Ti (CH)3CH2)3(i-C4H9) Tri (n-butyl) methyl titanium (Ti (CH))3)(C4H9)3) Di-n-butyldimethyl titanium (Ti (CH)3)2(C4H9)2) Trimethyl n-butyltitanium (Ti (CH)3)3(C4H9) Tri (n-butyl) methyl titanium (Ti (CH))3CH2)(C4H9)3) Di-n-butyldiethyltitanium (Ti (CH)3CH2)2(C4H9)2) Triethyl n-butyltitanium (Ti (CH)3CH2)3(C4H9) Etc.);
tetramethyl zirconium (Zr (CH)3)4) Tetraethyl zirconium (Zr (CH)3CH2)4) Tetraisobutylzirconium (Zr (i-C)4H9)4) Tetra-n-butylzirconium (Zr (C)4H9)4) Triethylmethylzirconium (Zr (CH)3)(CH3CH2)3) Diethyl dimethyl zirconium (Zr (CH)3)2(CH3CH2)2) Trimethylethylzirconium (Zr (CH)3)3(CH3CH2) Triisobutylzirconium methyl (Zr (CH))3)(i-C4H9)3) Diisobutyldimethylzirconium (Zr (CH)3)2(i-C4H9)2) Trimethylisobutylzirconium (Zr (CH)3)3(i-C4H9) Triisobutylethylzirconium (Zr (CH))3CH2)(i-C4H9)3) Diisobutyl diethyl zirconium (Zr (CH)3CH2)2(i-C4H9)2) Triethyl isobutyl zirconium (Zr (CH)3CH2)3(i-C4H9) Tri-n-butylzirconium (Zr (CH))3)(C4H9)3) Di-n-butylzirconium dimethyl (Zr (CH)3)2(C4H9)2) Trimethyl n-butyl zirconium (Zr (CH)3)3(C4H9) Tri-n-butylzirconium (Zr (CH))3CH2)(C4H9)3) Di-n-butyldiethylzirconium (Zr (CH)3CH2)2(C4H9)2) Triethyl n-butyl zirconium (Zr (CH)3CH2)3(C4H9) Etc.);
tetramethylhafnium (Hf (CH)3)4) Tetraethyl hafnium (Hf (CH)3CH2)4) Tetra isobutyl hafnium (Hf (i-C)4H9)4) Tetra-n-butyl hafnium (Hf (C)4H9)4) Triethylhafnium (Hf (CH)3)(CH3CH2)3) Diethyl hafnium (Hf (CH)3)2(CH3CH2)2) Trimethylhafnium (Hf (CH)3)3(CH3CH2) Triisobutyl methyl hafnium (Hf (CH)3)(i-C4H9)3) Diisobutyldimethylhafnium (Hf (CH)3)2(i-C4H9)2) Trimethylisobutylhafnium (Hf (CH)3)3(i-C4H9) Triisobutylethylhafnium (Hf (CH)3CH2)(i-C4H9)3) Diisobutyl hafnium diethyl (Hf (CH)3CH2)2(i-C4H9)2) Triethyl isobutyl hafnium (Hf (CH)3CH2)3(i-C4H9) Tri-n-butyl hafnium methyl (Hf (CH))3)(C4H9)3) Di-n-butyl hafnium dimethyl (Hf (CH)3)2(C4H9)2) Trimethyl-n-butyl-hafnium (Hf (CH)3)3(C4H9) Tri-n-butyl hafnium methyl (Hf (CH))3CH2)(C4H9)3) Di-n-butyl hafnium diethyl (Hf (CH)3CH2)2(C4H9)2) Triethyl n-butyl hafnium (Hf (CH)3CH2)3(C4H9) Etc.).
Examples of the group IVB metal alkoxide compound include tetramethoxytitanium (Ti (OCH)3)4) Tetraethoxytitanium (Ti (OCH)3CH2)4) Titanium tetraisobutoxide (Ti (i-OC)4H9)4) Titanium tetra-n-butoxide (Ti (OC)4H9)4) Triethoxymethoxy titanium (Ti (OCH)3)(OCH3CH2)3) Diethoxydimethoxy titanium (Ti (OCH)3)2(OCH3CH2)2) Trimethoxy ethoxy titanium (Ti (OCH)3)3(OCH3CH2) Triisobutoxymethoxy titanium (Ti (OCH)3)(i-OC4H9)3) Di-isobutoxy dimethoxy titanium (Ti (OCH)3)2(i-OC4H9)2) Trimethoxy isobutoxy titanium (Ti (OCH)3)3(i-OC4H9) B), 3Isobutoxyethoxy titanium (Ti (OCH)3CH2)(i-OC4H9)3) Di-isobutoxy diethoxy titanium (Ti (OCH)3CH2)2(i-OC4H9)2) Triethoxy isobutoxy titanium (Ti (OCH)3CH2)3(i-OC4H9) Tri (n-butoxy) methoxy titanium (Ti (OCH)3)(OC4H9)3) Di-n-butoxy dimethoxy titanium (Ti (OCH)3)2(OC4H9)2) Trimethoxy n-butoxy titanium (Ti (OCH)3)3(OC4H9) Tri (n-butoxy) methoxy titanium (Ti (OCH)3CH2)(OC4H9)3) Di-n-butoxydiethoxytitanium (Ti (OCH)3CH2)2(OC4H9)2) Titanium triethoxy n-butoxide (Ti (OCH)3CH2)3(OC4H9) Etc.);
tetramethoxyzirconium (Zr (OCH)3)4) Zirconium tetraethoxide (Zr (OCH)3CH2)4) Zirconium tetraisobutoxide (Zr (i-OC)4H9)4) Zirconium tetra-n-butoxide (Zr (OC)4H9)4) Triethoxymethoxy zirconium (Zr (OCH)3)(OCH3CH2)3) Diethoxydimethoxy zirconium (Zr (OCH)3)2(OCH3CH2)2) Trimethoxy zirconium ethoxide (Zr (OCH)3)3(OCH3CH2) Triisobutoxy methoxy zirconium (Zr (OCH)3)(i-OC4H9)3) Bis (isobutoxy) dimethoxy zirconium (Zr (OCH)3)2(i-OC4H9)2) Trimethoxy isobutoxy zirconium (Zr (OCH)3)3(i-C4H9) Triisobutoxyethoxyzirconium (Zr (OCH)3CH2)(i-OC4H9)3) Bis (isobutoxy) diethoxy zirconium (Zr (OCH)3CH2)2(i-OC4H9)2) Triethoxy isobutoxy zirconium (Zr (OCH)3CH2)3(i-OC4H9) Zirconium tri (n-butoxy) methoxy (Zr (OCH)3)(OC4H9)3) Di-n-butoxy dimethoxy zirconium (Zr (OCH)3)2(OC4H9)2) Trimethoxy n-butoxy zirconium (Zr (OCH)3)3(OC4H9) Zirconium tri (n-butoxy) methoxy (Zr (OCH)3CH2)(OC4H9)3) Di-n-butoxydiethoxy zirconium (Zr (OCH)3CH2)2(OC4H9)2) Triethoxy n-butoxy zirconium (Zr (OCH)3CH2)3(OC4H9) Etc.);
tetramethoxyhafnium (Hf (OCH)3)4) Hafnium tetraethoxide (Hf (OCH)3CH2)4) Tetra-isobutoxy hafnium (Hf (i-OC)4H9)4) Hafnium tetra-n-butoxide (Hf (OC)4H9)4) Triethoxy hafnium (Hf (OCH)3)(OCH3CH2)3) Diethoxy dimethoxy hafnium (Hf (OCH)3)2(OCH3CH2)2) Trimethoxyhafnium ethoxide (Hf (OCH)3)3(OCH3CH2) Triisobutoxy methoxy hafnium (Hf (OCH)3)(i-OC4H9)3) Di-isobutoxy dimethoxy hafnium (Hf (OCH)3)2(i-OC4H9)2) Trimethoxy isobutoxy hafnium (Hf (OCH)3)3(i-OC4H9) Triisobutoxyethoxyhafnium (Hf (OCH)3CH2)(i-OC4H9)3) Di-isobutoxy diethoxy hafnium (Hf (OCH)3CH2)2(i-OC4H9)2) Triethoxy isobutoxy hafnium (Hf (OCH)3CH2)3(i-C4H9) Tri (n-butoxy) methoxy hafnium (Hf (OCH)3)(OC4H9)3) Di-n-butoxy dimethoxy hafnium (Hf (OCH)3)2(OC4H9)2) Trimethoxy hafnium n-butoxide (Hf (OCH)3)3(OC4H9) Tri (n-butoxy) methoxy hafnium (Hf (OCH)3CH2)(OC4H9)3) Di-n-butoxy hafnium diethoxide (Hf (OCH)3CH2)2(OC4H9)2) Hafnium triethoxy-n-butoxide (Hf (OCH)3CH2)3(OC4H9) Etc.).
Examples of the group IVB metal alkyl halide include trimethyltitanium chloride (TiCl (CH)3)3) Triethyltitanium chloride (TiCl (CH))3CH2)3) Triisobutyltitanium chloride (TiCl (i-C))4H9)3) Tri-n-butyltitanium chloride (TiCl (C))4H9)3) Dimethyl titanium dichloride (TiCl)2(CH3)2) Diethyl titanium dichloride (TiCl)2(CH3CH2)2) Diisobutyl titanium dichloride (TiCl)2(i-C4H9)2) Tri-n-butyltitanium chloride (TiCl (C))4H9)3) Titanium trichloride methyl (Ti (CH)3)Cl3) Titanium trichloride ethyl (Ti (CH)3CH2)Cl3) Isobutyl titanium trichloride (Ti (i-C)4H9)Cl3) N-butyl titanium trichloride (Ti (C)4H9)Cl3)；
Trimethyl titanium bromide (TiBr (CH)3)3) Triethyltitanium bromide (TiBr (CH)3CH2)3) Triisobutyl titanium bromide (TiBr (i-C)4H9)3) Tri-n-butyl titanium bromide (TiBr (C)4H9)3) Titanium dimethyl dibromide (TiBr)2(CH3)2) Diethyl titanium dibromide (TiBr)2(CH3CH2)2) Diisobutyl titanium dibromide (TiBr)2(i-C4H9)2) Tri-n-butyl titanium bromide (TiB)r(C4H9)3) Titanium methyltrubromide (Ti (CH)3)Br3) Titanium ethyltribromide (Ti (CH)3CH2)Br3) Titanium isobutyltribromide (Ti (i-C)4H9)Br3) N-butyl titanium tribromide (Ti (C)4H9)Br3)；
Zirconium trimethyl chloride (ZrCl (CH)3)3) Triethylzirconium chloride (ZrCl (CH)3CH2)3) Triisobutyl zirconium chloride (ZrCl (i-C)4H9)3) Tri-n-butyl zirconium chloride (ZrCl (C)4H9)3) Zirconium dimethyldichloride (ZrCl)2(CH3)2) Diethyl zirconium dichloride (ZrCl)2(CH3CH2)2) Diisobutyl zirconium dichloride (ZrCl)2(i-C4H9)2) Tri-n-butyl zirconium chloride (ZrCl (C)4H9)3) Zirconium methyltrichloride (Zr (CH)3)Cl3) Zirconium ethyl trichloride (Zr (CH)3CH2)Cl3) Isobutyl zirconium trichloride (Zr (i-C)4H9)Cl3) N-butyl zirconium trichloride (Zr (C)4H9)Cl3)；
Zirconium trimethyl bromide (ZrBr (CH)3)3) Triethylzirconium bromide (ZrBr (CH)3CH2)3) Triisobutyl zirconium bromide (ZrBr (i-C)4H9)3) Tri-n-butyl zirconium bromide (ZrBr (C)4H9)3) Zirconium dimethyl dibromide (ZrBr)2(CH3)2) Diethyl zirconium dibromide (ZrBr)2(CH3CH2)2) Diisobutyl zirconium dibromide (ZrBr)2(i-C4H9)2) Tri-n-butyl zirconium bromide (ZrBr (C)4H9)3) Methyl zirconium tribromide (Zr (CH)3)Br3) Zirconium ethyl tribromide (Zr (CH)3CH2)Br3) Isobutyl zirconium tribromide (Zr (i-C)4H9)Br3) N-butyl zirconium tribromide (Zr (C)4H9)Br3)；
Trimethyl hafnium chloride (HfCl (CH)3)3) Triethyl hafnium chloride (HfCl (CH)3CH2)3) Triisobutylhafnium chloride (HfCl (i-C)4H9)3) Tri-n-butyl hafnium chloride (HfCl (C)4H9)3) Hafnium dimethyl dichloride (HfCl)2(CH3)2) Hafnium diethyldichloride (HfCl)2(CH3CH2)2) Diisobutyldimethium chloride (HfCl)2(i-C4H9)2) Tri-n-butyl hafnium chloride (HfCl (C)4H9)3) Hafnium methyl trichloride (Hf (CH)3)Cl3) Hafnium ethyl trichloride (Hf (CH)3CH2)Cl3) Isobutyl hafnium trichloride (Hf (i-C)4H9)Cl3) N-butyl hafnium trichloride (Hf (C)4H9)Cl3)；
Trimethyl hafnium bromide (HfBr (CH)3)3) Triethyl hafnium bromide (HfBr (CH)3CH2)3) Triisobutylbromide hafnium (HfBr (i-C)4H9)3) Tri-n-butyl hafnium bromide (HfBr (C)4H9)3) Hafnium dimethyl dibromide (HfBr)2(CH3)2) Hafnium diethyl dibromide (HfBr)2(CH3CH2)2) Diisobutyl hafnium dibromide (HfBr)2(i-C4H9)2) Tri-n-butyl hafnium bromide (HfBr (C)4H9)3) Hafnium methyl tribromide (Hf (CH)3)Br3) Hafnium ethyl tribromide (Hf (CH)3CH2)Br3) Isobutyl hafnium tribromide (Hf (i-C)4H9)Br3) N-butyl hafnium tribromide (Hf (C)4H9)Br3)。
Examples of the group IVB metal alkoxyhalide include trimethoxytitanium chloride (TiCl (OCH)3)3) Titanium triethoxide chloride (TiCl (OCH)3CH2)3) Triisobutoxy titanium chloride (TiCl (i-OC)4H9)3) Titanium tri-n-butoxide (TiCl (OC)4H9)3) Dimethoxy titanium dichloride (TiCl)2(OCH3)2) Diethoxytitanium dichloride (TiCl)2(OCH3CH2)2) Bis (isobutoxy) titanium dichloride (TiCl)2(i-OC4H9)2) Titanium tri-n-butoxide (TiCl (OC)4H9)3) Titanium methoxytrichloride (Ti (OCH)3)Cl3) Titanium ethoxide trichloride (Ti (OCH)3CH2)Cl3) Titanium (Ti (i-C)) trichloride (isobutoxy group)4H9)Cl3) Titanium (Ti (OC) chloride n-butoxide4H9)Cl3)；
Trimethoxy titanium bromide (TiBr (OCH)3)3) Titanium triethoxy bromide (TiBr (OCH)3CH2)3) Triisobutoxytitanium bromide (TiBr (i-OC)4H9)3) Titanium tri-n-butoxide bromide (TiBr (OC)4H9)3) Titanium dibromide dimethoxy (TiBr)2(OCH3)2) Diethoxy titanium dibromide (TiBr)2(OCH3CH2)2) Titanium diisobutoxy dibromide (TiBr)2(i-OC4H9)2) Titanium tri-n-butoxide bromide (TiBr (OC)4H9)3) Titanium methoxytribromide (Ti (OCH)3)Br3) Titanium ethoxytribromide (Ti (OCH)3CH2)Br3) Titanium (Ti (i-C)) isobutoxy tribromide4H9)Br3) Titanium n-butoxide tribromide (Ti (OC)4H9)Br3)；
Trimethoxy zirconium chloride (ZrCl (OCH)3)3) Zirconium triethoxy chloride (ZrCl (OCH)3CH2)3) Triisobutoxy zirconium chloride (ZrCl (i-OC)4H9)3) Zirconium tri-n-butoxide chloride (ZrCl (OC)4H9)3) Dimethoxy zirconium dichloride (ZrCl)2(OCH3)2) Diethyl oxideZirconium dichloride (ZrCl)2(OCH3CH2)2) Bis (isobutoxy) zirconium dichloride (ZrCl)2(i-OC4H9)2) Zirconium tri-n-butoxide chloride (ZrCl (OC)4H9)3) Zirconium oxychloride (Zr (OCH)3)Cl3) Zirconium ethoxy trichloride (Zr (OCH)3CH2)Cl3) Isobutoxy zirconium trichloride (Zr (i-C)4H9)Cl3) N-butoxy zirconium trichloride (Zr (OC)4H9)Cl3)；
Trimethoxy zirconium bromide (ZrBr (OCH)3)3) Zirconium triethoxy bromide (ZrBr (OCH)3CH2)3) Triisobutoxy zirconium bromide (ZrBr (i-OC)4H9)3) Zirconium tri-n-butoxide bromide (ZrBr (OC)4H9)3) Zirconium dimethoxydibromide (ZrBr)2(OCH3)2) Diethoxy zirconium dibromide (ZrBr)2(OCH3CH2)2) Zirconium diisobutoxy dibromide (ZrBr)2(i-OC4H9)2) Zirconium tri-n-butoxide bromide (ZrBr (OC)4H9)3) Zirconium (Zr) (OCH) tribromide3)Br3) Zirconium ethoxy tribromide (Zr (OCH)3CH2)Br3) Isobutoxy zirconium tribromide (Zr (i-C)4H9)Br3) N-butoxy zirconium tribromide (Zr (OC)4H9)Br3)；
Trimethoxyhafnium chloride (HfCl (OCH)3)3) Hafnium triethoxide chloride (HfCl (OCH)3CH2)3) Triisobutoxy hafnium chloride (HfCl (i-OC)4H9)3) Hafnium tri-n-butoxide chloride (HfCl (OC)4H9)3) Hafnium dimethoxy dichloride (HfCl)2(OCH3)2) Hafnium dichloride diethoxy (HfCl)2(OCH3CH2)2) Bis (isobutoxy) hafnium dichloride (HfCl)2(i-OC4H9)2) Hafnium tri-n-butoxide chloride (H)fCl(OC4H9)3) Hafnium methoxy trichloride (Hf (OCH)3)Cl3) Ethoxy hafnium trichloride (Hf (OCH)3CH2)Cl3) Isobutoxy hafnium trichloride (Hf (i-C)4H9)Cl3) N-butoxy hafnium trichloride (Hf (OC)4H9)Cl3)；
Trimethoxy hafnium bromide (HfBr (OCH)3)3) Hafnium triethoxide bromide (HfBr (OCH)3CH2)3) Triisobutoxy hafnium bromide (HfBr (i-OC)4H9)3) Hafnium tri-n-butoxide bromide (HfBr (OC)4H9)3) Hafnium dimethoxy dibromide (HfBr)2(OCH3)2) Hafnium diethoxy dibromide (HfBr)2(OCH3CH2)2) Hafnium bis (isobutoxy) bromide (HfBr)2(i-OC4H9)2) Hafnium tri-n-butoxide bromide (HfBr (OC)4H9)3) Hafnium methoxy tribromide (Hf (OCH)3)Br3) Hafnium ethoxy tribromide (Hf (OCH)3CH2)Br3) Isobutoxy hafnium tribromide (Hf (i-C)4H9)Br3) Hafnium n-butoxide tribromide (Hf (OC)4H9)Br3)。
As the group IVB metal compound, the group IVB metal halide is preferable, and TiCl is more preferable4、TiBr4、ZrCl4、ZrBr4、HfCl4And HfBr4Most preferably TiCl4And ZrCl4。
These group IVB metal compounds may be used singly or in combination in any ratio.
When the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment reaction can be carried out directly using the chemical treatment agent. When the chemical treatment agent is in a solid state at ordinary temperature, it is preferably used in the form of a solution for the sake of metering and handling convenience. Of course, when the chemical treatment agent is in a liquid state at ordinary temperature, the chemical treatment agent may be used in the form of a solution 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 modified carrier.
Specifically, C may be mentioned5-12Alkane, C5-12Cycloalkanes, halogen radicals C5-12Alkanes and halogenated C5-12Examples of the cycloalkane include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane and the like, with pentane, hexane, decane and cyclohexane being preferred, and hexane being most preferred.
These solvents may be used singly or in combination in any ratio.
In addition, the concentration of the chemical treatment agent in the solution thereof is not particularly limited, and may be appropriately selected as needed as long as it can achieve 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 chemical treatment agent may be used as it is, or may be prepared as a solution of the chemical treatment agent and then used.
In general, the molar concentration of the chemical treatment agent in the solution 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, dropped) to the modified carrier to be treated; in the case of using a liquid chemical treatment agent such as titanium tetrachloride, it is sufficient if a predetermined amount of the chemical treatment agent is added (preferably dropwise) directly (but also after preparation into a solution) to the modified carrier to be treated, and the chemical treatment reaction is carried out (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, washing and drying.
According to the present invention, the filtration, washing and drying may be carried out by a conventional method, wherein the solvent for washing may be the same solvent as that used for dissolving the chemical treatment agent. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, and most preferably 2 to 4 times.
According to the invention, as the chemical treatment agent, the amount is used such that the molar ratio of the magnesium compound (solid) in terms of Mg element to the chemical treatment agent in terms of ivb group metal (such as Ti) element is 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 the supported non-metallocene catalyst of the present invention further comprises the step of pretreating the modified support with a co-chemical treatment agent selected from the group consisting of aluminoxane, aluminum alkyl, or any combination thereof, prior to treating the modified support with the chemical treatment agent. Then, the chemical treatment with the chemical treatment agent is carried out in exactly the same manner as described above except that the modified carrier is replaced with the pretreated modified carrier.
The chemical assisting agent is specifically described below.
According to the present invention, examples of the chemical assisting 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 of the following general formula (II): - (Al (R) -O-)n+2-。
Figure BDA0001940198150000271
In the above formula, the radicals R, equal to or different from each other (preferably equal), are each independently selected from C1-C8Alkyl, 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 preferable, and methylaluminoxane and isobutylaluminoxane are further preferable.
These aluminoxanes may be used singly or in combination 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 from one another (preferably identical) and are each independently selected from C1-C8Alkyl groups, preferably methyl, ethyl and isobutyl, most preferably methyl.
Specifically, examples of the aluminum alkyl include trimethylaluminum (Al (CH)3)3) Triethylaluminum (Al (CH)3CH2)3) Tripropyl aluminum (Al (C)3H7)3) Triisobutylaluminum (Al (i-C)4H9)3) Tri-n-butylaluminum (Al (C)4H9)3) Triisopentylaluminum (Al (i-C)5H11)3) Tri-n-pentylaluminum (Al (C)5H11)3) Trihexylaluminum (Al (C)6H13)3) Triisohexylaluminum (Al (i-C)6H13)3) Diethyl methyl aluminum (Al (CH)3)(CH3CH2)2) And dimethyl ethyl aluminum (Al (CH)3CH2)(CH3)2) And the like, among which trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable, and triethylaluminum and triisobutylaluminum are most preferable.
These alkyl aluminum compounds may be used singly or in combination of two or more kinds in an arbitrary ratio.
According to the present invention, the chemical assistant may be the aluminoxane alone or the alkylaluminum alone, or an arbitrary mixture of the aluminoxane and the alkylaluminum may be used. The ratio of each component in the mixture is not particularly limited, and may be arbitrarily selected as needed.
According to the invention, the co-chemical treatment agent is generally used in the form of a solution. In preparing the solution of the chemical assisting agent, the solvent used at this time is not particularly limited as long as it can dissolve the chemical assisting agent and does not destroy (e.g., dissolve) the existing carrier structure of the carrier.
Specifically, the solvent includes, for example, C5-12Alkanes and halogenated C5-12Examples of the alkane include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane and the like, with pentane, hexane, decane and cyclohexane being preferred, and hexane being most preferred.
These solvents may be used singly or in combination in any ratio.
In addition, the concentration of the chemical assisting treatment agent in the solution thereof is not particularly limited, and may be appropriately selected as needed as long as it can achieve the pretreatment with a predetermined amount of the chemical assisting treatment agent.
As a method for carrying out the pretreatment, for example, a solution of the chemical assistant is prepared first, and then the chemical assistant solution (containing a predetermined amount of the chemical assistant) is metered (preferably, dropwise) into the modified carrier to be pretreated with the chemical assistant at a temperature of-30 to 60 ℃ (preferably, -20 to 30 ℃), or the modified carrier is metered into the chemical assistant solution, thereby forming a reaction mixture, which is reacted for 1 to 8 hours, preferably 2 to 6 hours, and most preferably 3 to 4 hours (with stirring if necessary). The pretreated product obtained is then separated from the reaction mixture by filtration, washing (1 to 6 times, preferably 1 to 3 times) and optional drying, or may be used directly in the subsequent reaction step as a mixture without separation. At this time, since the mixed solution already contains a certain amount of the solvent, the amount of the solvent involved in the subsequent reaction step can be reduced accordingly.
According to the invention, as the chemical co-treatment agent, the amount is such that the molar ratio of the magnesium compound (solid) in terms of Mg element to the chemical co-treatment agent in terms of Al element is 1: 0 to 1.0, preferably 1: 0 to 0.5, more preferably 1: 0.1-0.5.
It is known to the person skilled in the art that all the process steps described above are preferably carried out under substantially water-and oxygen-free conditions. By substantially water and oxygen free is meant that the water and oxygen content of the system is continuously less than 10 ppm. Moreover, the supported non-metallocene catalyst of the present invention generally needs to be stored under a slight positive pressure in a closed condition for later use after preparation.
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: 0.0002-0.4, more preferably 1: 0.0008 to 0.2, more preferably 1: 0.001 to 0.1, the ratio of the magnesium compound (solid) to tetrahydrofuran being 1 mol: 0.5-10L, preferably 1 mol: 1 to 8L, more preferably 1 mol: 2-6L, wherein the volume ratio of the precipitating agent 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 in terms of Mg element to the chemical treatment agent in terms of IVB group 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 a supported non-metallocene catalyst (sometimes also referred to as a supported non-metallocene olefin polymerization catalyst) made by the aforementioned method of preparing a magnesium single support segmented in situ supported non-metallocene catalyst.
In a further embodiment, the present invention relates to an olefin homo/copolymerization process, wherein an olefin is homo-or copolymerized using the magnesium single-support segmented in-situ supported non-metallocene catalyst of the present invention as a catalyst for olefin polymerization.
In the method for homo-or copolymerization of olefin according to the present invention, other matters (for example, polymerization reactor, amount of olefin, catalyst, and addition method of olefin) not specified except those specifically mentioned below can be directly applied to those conventionally known in the art without any particular limitation, and the explanation thereof is omitted here.
According to the homopolymerization/copolymerization method, the magnesium single-carrier segmented in-situ supported non-metallocene catalyst is used as a main catalyst, and one or more selected from aluminoxane, alkyl aluminum, halogenated alkyl aluminum, boroflurane, alkyl boron and alkyl boron ammonium salt are used as a cocatalyst, so that olefin homopolymerization or copolymerization is realized.
The main catalyst and the cocatalyst are added into the polymerization reaction system in a mode of firstly adding the main catalyst and then adding the cocatalyst, or firstly adding the cocatalyst and then adding the main catalyst, or firstly contacting and mixing the main catalyst and the cocatalyst and then adding the main catalyst together, or respectively 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 sequence in the same feeding pipeline, or can be added in sequence in multiple feeding pipelines, and when the main catalyst and the cocatalyst are added respectively and simultaneously, multiple feeding pipelines are selected. For continuous polymerization, it is preferred that multiple feed lines are fed continuously at the same time, while for batch polymerization, it is preferred that the two be mixed and fed together in the same feed line, or that the co-catalyst be fed first and then the main catalyst be fed in the same feed line.
According to the present invention, the reaction mode of the olefin homo/copolymerization method is not particularly limited, and those known in the art can be used, and examples thereof include a slurry method, an emulsion method, a solution method, a bulk method, a gas phase method, and the like, and among them, the slurry method and the gas phase method are preferable.
According to the invention, as the olefin, for example, C may be mentioned2～C10Monoolefins, diolefins, cyclic olefins, and other ethylenically unsaturated compounds.
Specifically, as the C2～C10Examples of the monoolefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-methyl-1-penteneOctene, 1-decene, 1-undecene, 1-dodecene, styrene, etc.; examples of the cyclic olefin include 1-cyclopentene, norbornene, and the like; examples of the diolefins include 1, 4-butadiene, 2, 5-pentadiene, 1, 6-hexadiene, norbornadiene, 1, 7-octadiene, and the like; 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 the olefins, while copolymerization refers to the polymerization between two or more of the olefins.
According to the invention, the cocatalyst is selected from the group consisting of aluminoxanes, alkylaluminums, haloalkylaluminums, borofluoroalkanes, alkylboron and alkylboroammoniums salts, of which aluminoxanes and alkylaluminums are preferred.
Examples of the aluminoxane include linear aluminoxanes represented by the following general formula (I-1): (R) (R) Al- (Al (R) -O)n-O-Al (R), and a cyclic aluminoxane represented by the following general formula (II-1): - (Al (R) -O-)n+2-。
Figure BDA0001940198150000301
In the above formula, the radicals R, equal to or different from each other (preferably equal), are each independently selected from C1-C8Alkyl, 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 preferable, methylaluminoxane and isobutylaluminoxane are further preferable, and methylaluminoxane is most preferable.
These aluminoxanes may be used singly or in combination 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 from one another (preferably identical) and are each independently selected from C1-C8Alkyl groups, preferably methyl, ethyl and isobutyl, most preferably methyl.
Specifically, examples of the aluminum alkyl include trimethylaluminum (Al (CH)3)3) Triethylaluminum (Al (CH)3CH2)3) Tripropyl aluminum (Al (C)3H7)3) Triisobutylaluminum (Al (i-C)4H9)3) Tri-n-butylaluminum (Al (C)4H9)3) Triisopentylaluminum (Al (i-C)5H11)3) Tri-n-pentylaluminum (Al (C)5H11)3) Trihexylaluminum (Al (C)6H13)3) Triisohexylaluminum (Al (i-C)6H13)3) Diethyl methyl aluminum (Al (CH)3)(CH3CH2)2) And dimethyl ethyl aluminum (Al (CH)3CH2)(CH3)2) And the like, among which trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum are preferable, triethylaluminum and triisobutylaluminum are further preferable, and triethylaluminum is most preferable.
These alkyl aluminum compounds may be used singly or in combination of two or more kinds in an arbitrary ratio.
As the halogenated alkylaluminum, the boroflurane, the alkylboron and the alkylboronium salt, those conventionally used in the art can be directly used without particular limitation.
In addition, according to the present invention, the cocatalyst may be used singly or in combination of a plurality of the above-mentioned cocatalysts in an arbitrary ratio as required, and is not particularly limited.
According to the present invention, depending on the reaction system of the method for homo/copolymerizing olefin, it may be necessary to use a polymerization solvent.
As the polymerization solvent, those conventionally used in the art for the homopolymerization/copolymerization of olefins can be used without particular limitation.
The solvent for polymerization includes, for example, C4-10Alkanes (e.g. butane, pentane, hexane, heptane, octane, nonane or decane, etc.), halogenated C1-10Alkanes (such as dichloromethane), 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 singly or in combination in any 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, and more preferably 1 to 3MPa, but is not limited thereto in some cases. According to the present invention, the polymerization temperature is generally from-40 ℃ to 200 ℃, preferably from 10 ℃ to 100 ℃, more preferably from 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 carried out in the presence of hydrogen or in the absence of hydrogen. When present, the partial pressure of hydrogen may be 0.01% to 99%, preferably 0.01% to 50% of the polymerization pressure, but is not limited thereto in some cases.
According to the invention, the molar ratio of the cocatalyst, expressed as aluminium or boron, to the supported non-metallocene catalyst, expressed as group ivb metal, when carrying out the olefin homo/copolymerization process, is generally 1: 1-1000, preferably 1: 1 to 500, more preferably 1: 10 to 500, but the present invention is not limited to this.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Bulk density of polymer (unit is g/cm)3) The determination of (A) is carried out according to the Chinese national standard GB 1636-79.
The content of IVB group metal (such as Ti) and Mg element in the magnesium single-carrier segmented in-situ supported non-metallocene catalyst is determined by adopting an ICP-AES method, and the content of a non-metallocene ligand is determined by adopting an element analysis method.
The polymerization activity of the catalyst was calculated as follows: after the polymerization reaction was completed, the polymerization product in the reaction tank was filtered and dried, and then the mass of the polymerization product was weighed, and the polymerization activity of the catalyst (unit is kg polymer/g catalyst or kg polymer/gCat) was expressed as a ratio of the mass of the polymerization product divided by the mass of the 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 by a high temperature dilution Ubbelohde viscometer method (capillary inner diameter 0.44mm, constant temperature bath medium 300 # silicone oil, solvent for dilution decahydronaphthalene, measurement temperature 135 ℃) in accordance with ASTM D4020-00 as a standard, and the viscosity-average molecular weight Mv of the polymer was calculated in accordance with the following formula.
Mv＝5.37×104×[η]1.37
Wherein η is an intrinsic viscosity.
The tetrahydrofuran content of the magnesium carrier is determined according to the following method: performing quantitative analysis by capillary gas chromatography, wherein the apparatus is Agilent 6890N type gas chromatograph, and is equipped with autosampler and hydrogen Flame Ionization Detector (FID); 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 1.4 ml/min; the split ratio is 70: 1; the sample amount is 0.2 ml; the test reagents were chromatographically pure tetrahydrofuran and ethanol, the relative retention times determined tetrahydrofuran to be 2.951min, ethanol to be 2.426min, the calibration factors determined tetrahydrofuran to be 3.5182, and ethanol to be 5.1289. Three solutions of tetrahydrofuran to be detected with different concentrations in ethanol are accurately prepared as standard samples, and under the condition of gas chromatography, correction factors of all components are calculated by an area normalization method to make a relational graph of tetrahydrofuran concentration index and actual concentration. Accurately weighing 0.5g of magnesium carrier, adding 20ml of ethanol reagent, stirring and dissolving for 30min at normal temperature, and filtering to obtain filtrate for later use. Under the condition of gas chromatography, adding a certain amount of filtrate into an automatic sample injector for automatic program sample injection measurement, calculating a filtrate tetrahydrofuran concentration index by dividing the peak area of the tetrahydrofuran to be measured by the normalized total area, substituting the index into a relational graph to obtain the actual tetrahydrofuran concentration, and finally converting to obtain the tetrahydrofuran content in the magnesium carrier.
Example 1
2.5g of anhydrous magnesium chloride (MgCl) as magnesium compound are weighed2) Adding a certain amount of tetrahydrofuran, heating to 60 ℃ to dissolve, adding a precipitant hexane to precipitate, filtering, collecting a solid product, washing 2 times by using hexane, wherein the amount of hexane used in each time is the same as that added in the previous step, drying the obtained solid product for 6 hours at 45 ℃ under the vacuum of 10mBar absolute, and then drying for 8 hours at 80 ℃ under the vacuum of 10mBar absolute to obtain the magnesium carrier, wherein the tetrahydrofuran content is 0.17 wt%.
Weighing 25ml of hexane solvent, adding the hexane solvent into the magnesium carrier, adding a hexane solution of the non-metallocene ligand under the stirring condition, reacting for 4 hours at 30 ℃, filtering, washing for 3 times by 25ml of hexane each time, and vacuumizing and drying for 6 hours at 30 ℃ and under the absolute pressure of 10mBar to obtain the modified carrier.
25ml of hexane solvent was measured, added to the modified support, and titanium tetrachloride (TiCl) was added dropwise over 15min under stirring4) And (3) reacting the hexane solution of the chemical treatment agent at 30 ℃ for 4h, filtering, washing with hexane for 3 times, wherein the volume of the hexane solution is 25ml each time, and finally, vacuumizing and drying at 30 ℃ under the absolute pressure of 10mBar for 12h to obtain the magnesium single-carrier segmented in-situ supported non-metallocene catalyst.
Wherein: the non-metallocene ligand adopts a structural formula as
Figure BDA0001940198150000341
The compound of (1).
The mixture ratio is as follows: the ratio of the magnesium compound to the hexane solvent for dissolving the magnesium compound is 1 mol: 4L; the molar ratio of the magnesium compound to the non-metallocene ligand is 1: 0.004; the volume ratio of the precipitant hexane to tetrahydrofuran is 1: 1; the molar ratio of the magnesium compound to the titanium tetrachloride which is a chemical treatment agent is 1: 0.20.
this catalyst is designated CAT-1.
Example 2
Essentially the same as example 1, with the following changes:
the magnesium compound solution was dried under vacuum at 35 ℃ and absolute pressure of 10mBar for 10h and then at 90 ℃ and absolute pressure of 10mBar for 6h without using a precipitant to obtain a magnesium carrier having a tetrahydrofuran content of 0.11 wt%.
This catalyst is designated as CAT-2.
Example 3
Essentially the same as example 1, with the following changes:
treating the modified support with a treatment chemical selected from triethylaluminum (Al (C)2H5)3) The chemical treatment assistant agent is used for pretreating the modified carrier.
25ml of hexane solvent was measured and added to the modified support obtained in example 1, and triethylaluminum (Al (C) as a chemical auxiliary was added dropwise within the first 15min under stirring2H5)3) After stirring and reacting for 1h, filtering, washing 2 times with hexane, 25ml each time, and vacuum-drying at 60 ℃ under an absolute pressure of 5mBar for 6h to obtain the pretreated modified carrier. The resulting pretreated modified carrier is used in the subsequent chemical treatment agent treatment step.
Wherein the molar ratio of the magnesium compound to the auxiliary chemical treatment agent is 1: 0.35.
this catalyst is designated as CAT-3.
Example 4
Essentially the same as example 3, with the following changes:
the chemical assistant treating agent is Methyl Aluminoxane (MAO).
Wherein: the molar ratio of the magnesium compound to the auxiliary chemical treatment agent is 1: 0.5.
this catalyst is designated as CAT-4.
Example 5
Essentially the same as example 1, with the following changes:
the solid product obtained was dried at a temperature of 40 ℃ under vacuum of absolute pressure 10mBar for 8h and then at a temperature of 70 ℃ under vacuum of absolute pressure 10mBar for 8h to obtain a magnesium support having a tetrahydrofuran content of 0.30 wt.%.
This catalyst is designated as CAT-5.
Comparative example A
Essentially the same as example 1, with the following changes:
adding precipitant hexane into the magnesium compound solution to precipitate, filtering, washing for 2 times, wherein the amount of precipitant is the same as that of the previous precipitant, uniformly heating the obtained solid product to 110 deg.C, and drying under vacuum of absolute pressure 10mBar for 24h to obtain magnesium carrier with tetrahydrofuran content of 0.03 wt%.
The catalyst is denoted as CAT-A.
Comparative example B
Essentially the same as example 1, with the following changes:
the solid product obtained was dried under vacuum at 20 ℃ and an absolute pressure of 10mBar for 1h to obtain a magnesium support with a tetrahydrofuran content of 1.48 wt%.
The catalyst is denoted as CAT-B.
Example 6
5g of the magnesium compound magnesium ethoxide (Mg (OC)2H5)2) Adding a certain amount of tetrahydrofuran, heating to 60 ℃ to dissolve, adding decane as a precipitant to precipitate, filtering, collecting a solid product, washing 2 times by using decane, wherein the using amount of decane in each time is the same as that of the decane added in the previous step, drying the obtained solid product for 4 hours at 50 ℃ under the vacuum of 5mBar absolute, and then drying for 12 hours at 90 ℃ under the vacuum of 5mBar absolute to obtain the magnesium carrier, wherein the tetrahydrofuran content is 0.23 wt%.
Measuring 50ml of decane solvent, adding the decane solvent into the magnesium carrier, adding decane solution of non-metallocene ligand under the stirring condition, reacting for 4h at 30 ℃, filtering, washing for 3 times by 50ml each time by decane, and vacuumizing and drying for 6h at 60 ℃ under the absolute pressure of 5mBar to obtain the modified carrier.
50ml of decane solvent was measured, added to the modified carrier, and titanium tetrachloride (TiCl) was added dropwise over 15min under stirring4) Decane solution of chemical treatment agent, reaction at 30 deg.C for 4 hr, filtering, washing with decaneWashing for 3 times, 50ml each time, and finally vacuumizing and drying for 16h at 60 ℃ and under the absolute pressure of 5mBar to obtain the magnesium single-carrier segmented in-situ supported non-metallocene catalyst.
Wherein: the non-metallocene ligand adopts a structural formula as
Figure BDA0001940198150000361
The compound of (1).
The mixture ratio is as follows: the ratio of the magnesium compound to the tetrahydrofuran is 1 mol: 6L; the molar ratio of the magnesium compound to the non-metallocene ligand is 1: 0.01; the volume ratio of decane as a precipitant to tetrahydrofuran is 1: 1.4; the molar ratio of the magnesium compound to the titanium tetrachloride which is a chemical treatment agent is 1: 0.26.
this catalyst is designated as CAT-6.
Comparative example C
Essentially the same as example 6, with the following changes:
the obtained solid product was uniformly heated to 110 ℃ and dried under vacuum at an absolute pressure of 5mBar for 24 hours to obtain a magnesium carrier having a tetrahydrofuran content of 0.04 wt%.
The catalyst is denoted as CAT-C.
Comparative example D
Essentially the same as example 6, with the following changes:
the solid product obtained was dried at 20 ℃ under vacuum of 5mBar abs for 1h to obtain a magnesium support with a tetrahydrofuran content of 1.37 wt%.
The catalyst is noted as CAT-D.
Example 7 (application example)
Respectively weighing the magnesium single-carrier segmented in-situ supported non-metallocene catalysts CAT-1-6 and CAT-A-D, and respectively carrying out homopolymerization and copolymerization on ethylene and preparing the ultra-high molecular weight polyethylene with a cocatalyst (triethyl aluminum, methylaluminoxane or triisobutyl aluminum) according to the following methods under the following conditions.
The homopolymerization is as follows: 5L of polymerization autoclave, slurry polymerization process, 2.5L of hexane solvent, total polymerization pressure of 0.8MPa, polymerization temperature of 85 ℃, hydrogen partial pressure of 0.2MPa and reaction time of 2 h. Firstly, adding 2.5L of hexane into a polymerization autoclave, starting stirring, then adding a mixture of 20mg of magnesium single-carrier segmented in-situ supported non-metallocene catalyst and cocatalyst, then adding hydrogen to 0.2MPa, and finally continuously introducing ethylene to ensure that the total polymerization pressure is constant at 0.8 MPa. After the reaction is finished, the gas in the kettle is emptied, the polymer in the kettle is discharged, and the mass is weighed after drying. The details of the polymerization reaction and the results of the polymerization evaluation are shown in Table 1.
Copolymerization is as follows: 5L of polymerization autoclave, slurry polymerization process, 2.5L of hexane solvent, total polymerization pressure of 0.8MPa, polymerization temperature of 85 ℃, hydrogen partial pressure of 0.2MPa and reaction time of 2 h. Firstly, adding 2.5L of hexane into a polymerization autoclave, starting stirring, then adding a mixture of 20mg of magnesium single-carrier segmented in-situ supported non-metallocene catalyst and cocatalyst, adding 50g of hexene-1 comonomer at one time, then adding hydrogen to 0.2MPa, and finally continuously introducing ethylene to ensure that the total polymerization pressure is constant at 0.8 MPa. After the reaction is finished, the gas in the kettle is emptied, the polymer in the kettle is discharged, and the mass is weighed after drying. The details of the polymerization reaction and the results of the polymerization evaluation are shown in Table 1.
The preparation of the ultra-high molecular weight polyethylene comprises the following polymerization steps: 5L of polymerization autoclave, slurry polymerization process, 2.5L of hexane solvent, total polymerization pressure of 0.5MPa, polymerization temperature of 70 ℃ and reaction time of 6 h. Firstly, adding 2.5L of hexane into a polymerization autoclave, starting stirring, then adding a mixture of 20mg of magnesium single-carrier segmented in-situ supported non-metallocene catalyst and a cocatalyst, wherein the molar ratio of the cocatalyst to active metal of the catalyst is 100, and finally continuously introducing ethylene to ensure that the total polymerization pressure is constant at 0.5 MPa. After the reaction is finished, the gas in the kettle is emptied, the polymer in the kettle is discharged, and the mass is weighed after drying. The details of the polymerization reaction and the results of the polymerization evaluation are shown in Table 2.
TABLE 1 summary of the effects of magnesium single-carrier segmented in-situ supported non-metallocene catalysts for olefin polymerization
Figure BDA0001940198150000381
TABLE 2 summary of polymerization reaction effect of magnesium single-carrier segmented in-situ supported non-metallocene catalyst for preparing ultra-high molecular weight polyethylene
Figure BDA0001940198150000382
From comparison of the effects obtained by numbers 1 and 3 in table 1, it is understood that the copolymerization effect of the catalyst is remarkable, that is, the copolymerization activity of the catalyst is higher than that of the homopolymerization, and the copolymerization 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 results obtained by the numbers 1 and 2 in Table 1, the molar ratio of the cocatalyst to the active metal of the catalyst required in the polymerization process is 50 and 100, and the obtained polymerization performance is equivalent, thus indicating that the catalyst provided by the present invention requires a smaller amount of cocatalyst when used for olefin polymerization.
As can be seen from comparison of numbers 1, 2, 4, 7-8 and 9-12 in Table 1 and numbers 1, 2, 3 and 4 in Table 2, the catalysts obtained by controlling the tetrahydrofuran content in the magnesium carrier during the preparation process of the catalysts of the present invention have better catalytic activity, polymer bulk density, and viscosity-average molecular weight of ultra-high molecular weight polyethylene than those obtained when the magnesium carrier is completely dried or the tetrahydrofuran content is higher.
Although 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 appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.

Claims (13)

1. A preparation method of a magnesium single-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 drying the magnesium compound solution, or adding a precipitant to the magnesium compound solution and drying the obtained solid product to obtain a magnesium carrier, wherein the tetrahydrofuran content in the magnesium carrier is 0.10 to 0.50 wt%, preferably 0.10 to 0.35 wt%, more preferably 0.11 to 0.25 wt%;
treating the magnesium carrier with a non-metallocene ligand to obtain a modified carrier; and
and treating the modified carrier with a chemical treatment agent selected from IVB group metal compounds to obtain the magnesium single carrier segmented in-situ supported non-metallocene catalyst.
2. The method of claim 1, further comprising the step of pretreating the modified support with a co-chemical treatment agent selected from the group consisting of alumoxanes, aluminum alkyls, or any combination thereof, prior to treating the modified support with the chemical treatment agent.
3. The production method according to claim 1 or 2, wherein the magnesium compound is selected from one or more of magnesium halide, alkoxy magnesium, alkyl magnesium halide and alkyl alkoxy magnesium, preferably from one or more of magnesium halide and alkoxy magnesium, more preferably magnesium chloride and/or magnesium ethoxide.
4. The method of claim 1, wherein the non-metallocene ligand is selected from one or more of the compounds having the following chemical structural formula:
Figure RE-FDA0001989354850000011
preferably one or more selected from the group consisting of compound (a) and compound (B) having the following chemical structural formula:
Figure RE-FDA0001989354850000021
more preferably one or more selected from the group consisting of compounds (A-1) to (A-4) and compounds (B-1) to (B-4) having the following chemical structural formulae:
Figure RE-FDA0001989354850000022
Figure RE-FDA0001989354850000031
in all of the above chemical structural formulae,
q is 0 or 1;
d is 0 or 1;
a is selected from oxygen atom, sulfur atom, selenium atom,
Figure RE-FDA0001989354850000032
-NR23R24、-N(O)R25R26、
Figure RE-FDA0001989354850000033
-PR28R29、-P(O)R30OR31Sulfone group, sulfoxide group or-Se (O) R39Wherein N, O, S, Se and P are each coordinating atoms;
b is selected from nitrogen atom, nitrogen-containing group, phosphorus-containing group or C1－C30A hydrocarbyl group;
d is selected from nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing group, C1－C30A 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, 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 C1－C30Hydrocarbyl, substituted C1－C30A hydrocarbon radical orAn inert functional group;
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 a coordinating atom;
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 single bond or a double bond;
-represents a covalent or ionic bond;
R1to R4、R6To R21Each independently selected from hydrogen and C1－C30Hydrocarbyl, substituted C1－C30Hydrocarbon radicals or inert functional groups, R22To R36、R38And R39Each independently selected from hydrogen and C1－C30Hydrocarbyl or substituted C1－C30A hydrocarbon group, the above groups may be the same or different from each other, and adjacent groups may be bonded to each other to form a bond or a ring, preferably an aromatic ring;
the inert functional group is selected from the group consisting of halogen, oxygen-containing group, nitrogen-containing group, silicon-containing group, germanium-containing group, sulfur-containing group, tin-containing group, C1－C10Ester groups and nitro groups;
R5selected from lone pair of electrons on nitrogen, hydrogen, C1－C30Hydrocarbyl, substituted C1－C30A hydrocarbyl group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group; when R is5When it is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R5N, O, S, P and Se in (1) can be used as coordination atoms;
said substituted C1－C30The hydrocarbon radical being selected from the group containing one or more halogens or C1－C30C with alkyl as substituent1－C30A hydrocarbon group,
the non-metallocene ligand is further preferably selected from one or more of the compounds having the following chemical structural formula:
Figure RE-FDA0001989354850000041
Figure RE-FDA0001989354850000051
the non-metallocene ligand is most preferably selected from one or more of the compounds having the following chemical structural formula:
Figure RE-FDA0001989354850000052
5. the production method according to claim 4,
the halogen is selected from F, Cl, Br or I;
the nitrogen-containing group is selected from
Figure RE-FDA0001989354850000053
-NR23R24、-T-NR23R24or-N (O) R25R26；
The phosphorus-containing group is selected from
Figure RE-FDA0001989354850000054
-PR28R29、-P(O)R30R31or-P (O) R32(OR33)；
The oxygen-containing group is selected from hydroxyl, -OR34and-T-OR34；
The sulfur-containing group is selected from-SR35、-T-SR35、-S(O)R36or-T-SO2R37；
The selenium-containing group is selected from-SeR38、-T-SeR38、-Se(O)R39or-T-Se (O) R39；
The group T is selected from C1－C30Hydrocarbyl or substituted C1－C30Hydrocarbyl radical；
The R is37Selected from hydrogen, C1－C30Hydrocarbyl or substituted C1－C30A hydrocarbyl group;
said C is1－C30The hydrocarbon radical being selected from C1－C30Alkyl radical, C7－C30Alkylaryl group, C7－C30Aralkyl radical, C3－C30Cyclic alkyl, C2－C30Alkenyl radical, C2－C30Alkynyl, C6－C30Aryl radical, C8－C30Condensed ring radicals or C4－C30A heterocyclic group, wherein the heterocyclic group contains 1 to 3 hetero atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom;
the silicon-containing group is selected from-SiR42R43R44or-T-SiR45；
The germanium-containing group is selected from-GeR46R47R48or-T-GeR49；
The tin-containing group is selected from-SnR50R51R52、-T-SnR53or-T-Sn (O) R54；
The R is42To R54Each independently selected from hydrogen, C1－C30Hydrocarbyl or substituted C as hereinbefore described1－C30A hydrocarbon group, the above groups may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a bond or form a ring, and
the group T is as defined above.
6. The process according to claims 1 to 5, wherein the precipitant is selected from one or more of an alkane, a cycloalkane, a halogenated alkane and a halogenated cycloalkane, preferably from one or more of pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoheptane, tribromomethane, tribromoethane, tribromobutane, chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane and bromocyclodecane, further preferably from one or more of hexane, heptane, decane and cyclohexane, most preferred are hexane and decane.
7. The process of claims 1-6, wherein the group IVB metal compound is selected from one or more of group IVB metal halides, group IVB metal alkyls, group IVB metal alkoxides, group IVB metal alkyl halides and group IVB metal alkoxyhalides, preferably from one or more of group IVB metal halides, more preferably from TiCl4、TiBr4、ZrCl4、ZrBr4、HfCl4And HfBr4Most preferably selected from TiCl4And ZrCl4One or more of (a).
8. The process according to claims 1 to 7, characterized in that the molar ratio of the magnesium compound to the non-metallocene ligand, expressed as Mg element, is 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferably 1: 0.0008 to 0.2, more preferably 1: 0.001 to 0.1, the ratio of the magnesium compound to tetrahydrofuran being 1 mol: 0.5-10L, preferably 1 mol: 1 to 8L, more preferably 1 mol: 2-6L, wherein the volume ratio of the precipitating agent 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 in terms of Mg element to the chemical treatment agent in terms of IVB group metal element is 1: 0.01-1, preferably 1: 0.01 to 0.50, more preferably 1: 0.10-0.30.
9. The process according to claim 2, wherein the aluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, more preferably from one or more of methylaluminoxane and isobutylaluminoxane, and the alkylaluminum is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, trihexylaluminum, triisohexylaluminum, diethylmethylaluminum and dimethylethylaluminum, preferably from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, and most preferably from one or more of triethylaluminum and triisobutylaluminum.
10. The production method according to claim 2 or 9, wherein the molar ratio of the magnesium compound in terms of Mg element to the chemical co-processing agent in terms of Al element is 1: 0 to 1.0, preferably 1: 0 to 0.5, more preferably 1: 0.1-0.5.
11. The production method according to claims 1 to 10, wherein the step of obtaining the magnesium carrier is performed in the following manner:
drying the magnesium compound solution at a temperature of 15-60 ℃, preferably 35-55 ℃, under a vacuum of 2-100mBar absolute, preferably 5-50mBar absolute, for a period of 2-30h, preferably 4-12h, and then at a temperature of 65-100 ℃, preferably 70-90 ℃, under a vacuum of 2-100mBar absolute, preferably 5-50mBar absolute, for a period of 1-20h, preferably 2-8h, to obtain the magnesium support,
alternatively, the magnesium support is obtained by adding a precipitant to a solution of the magnesium compound and drying the obtained solid product (optionally after washing) at a temperature of 15-60 ℃, preferably 35-55 ℃, under a vacuum of 2-100mBar absolute pressure, preferably 5-50mBar, for 2-30h, preferably 4-12h, and then at a temperature of 65-100 ℃, preferably 70-90 ℃, under a vacuum of 2-100mBar absolute pressure, preferably 5-50mBar, for 1-20h, preferably 2-8 h.
12. A magnesium single-carrier segmented in-situ supported non-metallocene catalyst, which is prepared by the preparation method according to any one of claims 1 to 11.
13. An olefin polymerization method, characterized by comprising a step of homopolymerizing or copolymerizing olefins using the magnesium single-carrier segmented in-situ supported non-metallocene catalyst according to claim 12 as a main catalyst and one or more selected from the group consisting of aluminoxane, alkylaluminum, haloalkylaluminum, boroflurane, alkylboron, and alkylboron ammonium salt as a co-catalyst.
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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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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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