A supported non-metallocene catalyst, its preparation method and use

Abstract

The present application relates to a kind of magnesium carrier supported non-metallocene catalyst, its preparation method and application.The preparation method of the magnesium carrier supported non-metallocene catalyst includes the following steps: magnesium compound and non-metallocene ligand are dissolved in alcohol, then diluent solvent is added, after mixing, dry, obtain the step of magnesium carrier, wherein the content of alcohol in magnesium carrier is 1.0-3.0wt%, preferably 1.1-2.5wt%, more preferably 1.5-2.0wt% relative to the weight of magnesium carrier;Alkyl aluminum is added to magnesium carrier and reacted, after filtration, obtain the step of magnesium-aluminum carrier;At-40~10 ℃, preferably-20~0 ℃, with the chemical treatment agent selected from group IVB metal compound, the magnesium-aluminum carrier is treated, obtain the step of the magnesium carrier supported non-metallocene catalyst.The supported non-metallocene catalyst has the characteristics such as simple and easy to operate and polymerization activity flexible adjustable.

Description

TECHNICAL FIELD

[0001] The present application relates to a non-metallocene catalyst. In particular, the present application relates to a supported non-metallocene catalyst, its preparation method and its application in olefin homopolymerization / copolymerization. BACKGROUND

[0002] The non-metallocene catalyst, also known as post-metallocene catalyst, appeared in the mid and late 1990s. The central atom of the main catalyst includes almost all transition metal elements. It is the fourth generation of olefin polymerization catalyst after Ziegler, Ziegler-Natta and metallocene catalyst. In some properties, it has reached or even exceeded the metallocene catalyst. The non-metallocene catalyst does not contain a cyclopentadienyl group, and the coordination atom is oxygen, nitrogen, sulfur and phosphorus. Its characteristics are that the central ion has strong electrophilicity, and has a cis-alkyl or halogen metal center structure, which is easy to carry out olefin insertion and σ-bond transfer, and the central metal is easy to alkylate, which is conducive to the generation of cationic active center; the formed complex has a limited geometric configuration, and the stereoselectivity, electronegativity and chirality can be adjusted. In addition, the metal-carbon bond formed is easy to polarize, which is beneficial to the polymerization of olefin. Therefore, even at a relatively high polymerization reaction temperature, a high molecular weight olefin polymer can be obtained.

[0003] However, the homogeneous olefin polymerization catalyst has been proved to have the disadvantages of short activity duration, easy to stick to the kettle, high methylaluminoxane consumption, and too low or too high molecular weight of the obtained polymer, which seriously limits its industrial application.

[0004] The olefin homopolymerization / copolymerization catalyst or catalyst system prepared in patents ZL01126323.7, ZL02151294.9 and ZL02110844.7 has a wide range of olefin homopolymerization / copolymerization performance and is suitable for various forms of polymerization processes. However, a high amount of cocatalyst is required for the catalyst or catalyst system disclosed in the patents to obtain suitable olefin polymerization activity, and there is a phenomenon of sticking to the kettle during polymerization.

[0005] The common practice is to prepare a supported catalyst by certain loading technology, so as to improve the polymerization performance of olefin and the particle morphology of the obtained polymer. It is shown that the initial activity of the catalyst is appropriately reduced to a certain extent, the polymerization activity life of the catalyst is prolonged, the caking or violent polymerization phenomenon during polymerization is reduced or even avoided, the morphology of the polymer is improved, and the apparent density of the polymer is increased, so that it can meet more polymerization processes, such as gas phase polymerization or slurry polymerization, etc.

[0006] Although using silica gel carriers or composite carriers containing silica gel as carriers for non-metallocene catalysts can polymerize to obtain polymers with good particle morphology and can control the polymer particle size distribution, the polymerization activity of the catalyst is low. Since the ash contains silica gel, the application range of the polymer is limited.

[0007] Chinese patent CN200710162676.0 discloses a supported non-metallocene catalyst and a method for preparing the catalyst. The catalyst is obtained by directly contacting a non-metallocene ligand with a magnesium compound containing a catalytically active metal via an in-situ loading method. However, the contact between the catalytically active metal and the magnesium compound described herein refers to adding a Group IVB metal compound to a preformed magnesium compound solid (e.g., a magnesium compound solid or a modified magnesium compound solid). This contact does not allow for a full reaction between the catalytically active metal and the magnesium compound. The resulting magnesium compound support containing the catalytically active metal is inevitably heterogeneous, lacking sufficient intermolecular contact and reaction, thereby limiting the effectiveness of the subsequently added non-metallocene ligand.

[0008] Similarly, Chinese patent CN200710162667.1 discloses a supported non-metallocene catalyst and its preparation method, which also has similar problems. It is obtained by directly contacting a catalytically active metal compound with a magnesium compound containing a non-metallocene ligand through an in-situ loading method. However, the contact described therein refers to adding a non-metallocene ligand solution to a formed magnesium compound solid (such as a magnesium compound solid or a modified magnesium compound solid). Such contact cannot achieve a full reaction between the non-metallocene ligand and the magnesium compound. The resulting magnesium compound support containing the non-metallocene ligand is inevitably heterogeneous, not fully contacting and reacting between molecules, thereby limiting the role of the non-metallocene ligand.

[0009] Chinese patent CN200910210990.0 discloses a method for preparing a supported non-metallocene catalyst, comprising the following steps: 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 support; and treating the modified support with a chemical treatment agent selected from Group IVB metal compounds to obtain the supported non-metallocene catalyst. The disclosure indicates that the alcohol introduced serves only as a cosolvent for the magnesium compound and the non-metallocene ligand and is subsequently removed during the drying process.

[0010] Chinese patent CN201710814678.7 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; a step of drying the magnesium compound solution or adding a precipitating agent to the magnesium compound solution to obtain a modified carrier, wherein the content of the alcohol in the modified carrier is 3.0-5.0 wt%; and a step of treating the modified carrier with a chemical treatment agent selected from a group IVB metal compound to obtain the supported non-metallocene catalyst.

[0011] The common problem of the supported non-metallocene catalysts in the prior art is that the olefin polymerization activity is low, and in order to improve the activity, a higher amount of cocatalyst must be used. Moreover, the prior art uses silica gel or the like as a support carrier, so that the content of ash in the polymer obtained by polymerization is high, thereby limiting the actual use of the polymer. The catalyst supported by the magnesium compound also limits the substantial improvement of the catalyst activity due to the heterogeneous composition and distribution formed in the preparation process.

[0012] Therefore, the current situation is that there is still a need for a supported non-metallocene catalyst which has a simple preparation method, is suitable for industrial production, and can overcome the problems existing in the prior art supported non-metallocene catalysts. SUMMARY

[0013] The present inventors have found, on the basis of the prior art, through catalyst preparation research, polymerization tests and performance analysis, that the use of the supported non-metallocene catalyst manufactured by the manufacturing method of the present application can well solve the aforementioned problems, thereby completing the present application.

[0014] In the preparation method of the supported non-metallocene catalyst of the present application, 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 application, no electron donor (such as the single ester, double ester, diether, diketone and diol ester compounds conventionally used for this purpose in the art) is added, and no ether solvent such as tetrahydrofuran is used in the preparation process. Furthermore, in the preparation method of the supported non-metallocene catalyst of the present application, no harsh reaction requirements and reaction conditions are required. Therefore, the preparation method of the supported catalyst is simple and is very suitable for industrial production.

[0015] Specifically, the present application relates to a preparation method of a magnesium carrier supported non-metallocene catalyst, comprising the following steps:

[0016] The step of dissolving the magnesium compound and the non-metallocene ligand in alcohol, adding dilution solvent, mixing and drying to obtain the magnesium carrier, wherein the content of alcohol in the magnesium carrier is 1.0-3.0 wt%, preferably 1.1-2.5 wt%, more preferably 1.5-2.0 wt% relative to the weight of the magnesium carrier; the step of adding alkyl aluminum to the magnesium carrier to react, and filtering to obtain the magnesium-aluminum carrier; the step of treating the magnesium-aluminum carrier with a chemical treatment agent selected from the group consisting of Group IVB metal compounds at -40-10°C, preferably -20-0°C to obtain the magnesium carrier supported non-metallocene catalyst.

[0017] The present application also relates to the magnesium carrier supported non-metallocene catalyst prepared by the preparation method, and the application of the catalyst in olefin homopolymerization / copolymerization.

[0018] Technical effects

[0019] The in-situ preparation method of the magnesium carrier supported non-metallocene catalyst of the present application is simple and feasible, the non-metallocene ligand is uniformly distributed in the magnesium carrier, and the loading amount of the non-metallocene ligand can be adjusted.

[0020] The magnesium carrier supported non-metallocene catalyst prepared by the present application has a significant copolymerization effect, i.e. the copolymerization activity of the catalyst is higher than the homopolymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, i.e. improve the particle morphology of the polymer.

[0021] Using the magnesium carrier supported non-metallocene catalyst provided by the present application, under the homopolymerization reaction condition without hydrogen, the ultra-high molecular weight polyethylene with high molecular weight can be polymerized.

[0022] Moreover, using the magnesium carrier supported non-metallocene catalyst provided by the present application, the polymer obtained by polymerization has fine average particle size, uniform distribution and low fine powder content. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 is the graph of the particle size distribution of the polymer of Example Part Table 2 No. 1.

[0024] Figure 2 is the graph of the particle size distribution of the polymer of Example Part Table 2 No. 4. DETAILED DESCRIPTION

[0025] The specific embodiments of the present application are described in detail below, but it should be pointed out that the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims in the appendix.

[0026] In the context of the present application, unless otherwise specifically 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 (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) has the same meaning as when preceded by the prefix "n-". For example, propyl is generally understood to be n-propyl, and butyl is generally understood to be n-butyl.

[0027] In the context of the present application, unless otherwise specifically stated, the physical property values (such as boiling point) of a substance are measured at normal temperature (25°C) and normal pressure (101325 Pa).

[0028] The steps for obtaining the magnesium support are described in detail below.

[0029] The method for preparing the magnesium support type non-metallocene catalyst of the present application includes the steps of dissolving a magnesium compound and a non-metallocene ligand in an alcohol, and then adding a dilution solvent, mixing and drying, thereby obtaining the magnesium support, wherein the content of the alcohol in the magnesium support is 1.0 to 3.0 wt%, preferably 1.1 to 2.5 wt%, and more preferably 1.5 to 2.0 wt% with respect to the weight of the magnesium support.

[0030] According to the present application, the term "magnesium compound" is used in the general concept of the art, and refers to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a support for a supported olefin polymerization catalyst.

[0031] According to the present application, as the magnesium compound, for example, magnesium halide, alkoxy magnesium halide, alkoxy magnesium, alkyl magnesium, alkyl magnesium halide, and alkyl alkoxy magnesium can be mentioned.

[0032] Specifically, as the magnesium halide, for example, magnesium chloride (MgCl2), magnesium bromide (MgBr2), magnesium iodide (MgI2), and magnesium fluoride (MgF2), etc. can be mentioned, of which magnesium chloride is preferred.

[0033] As the alkylmagnesium halide, for example, there can be mentioned methylmagnesium chloride (Mg(CH3)Cl), ethylmagnesium chloride (Mg(C2H5)Cl), propylmagnesium chloride (Mg(C3H7)Cl), n-butylmagnesium chloride (Mg(C4H9)Cl), isobutylmagnesium chloride (Mg(i-C4H9)Cl), methylmagnesium bromide (Mg(CH3)Br), ethylmagnesium bromide (Mg(C2H5)Br), propylmagnesium bromide (Mg(C3H7)Br), n-butylmagnesium bromide (Mg(C4H9)Br), isobutylmagnesium bromide (Mg(i-C4H9)Br), methylmagnesium iodide (Mg(CH3)I), ethylmagnesium iodide (Mg(C2H5)I), propylmagnesium iodide (Mg(C3H7)I), n-butylmagnesium iodide (Mg(C4H9)I), isobutylmagnesium iodide (Mg(i-C4H9)I), and the like, of which methylmagnesium chloride, ethylmagnesium chloride and isobutylmagnesium chloride are preferred.

[0034] As the alkylmagnesium halide, for example, there can be mentioned methylmagnesium chloride (Mg(CH3)Cl), ethylmagnesium chloride (Mg(C2H5)Cl), propylmagnesium chloride (Mg(C3H7)Cl), n-butylmagnesium chloride (Mg(C4H9)Cl), isobutylmagnesium chloride (Mg(i-C4H9)Cl), methylmagnesium bromide (Mg(CH3)Br), ethylmagnesium bromide (Mg(C2H5)Br), propylmagnesium bromide (Mg(C3H7)Br), n-butylmagnesium bromide (Mg(C4H9)Br), isobutylmagnesium bromide (Mg(i-C4H9)Br), methylmagnesium iodide (Mg(CH3)I), ethylmagnesium iodide (Mg(C2H5)I), propylmagnesium iodide (Mg(C3H7)I), n-butylmagnesium iodide (Mg(C4H9)I), isobutylmagnesium iodide (Mg(i-C4H9)I), and the like, of which methylmagnesium chloride, ethylmagnesium chloride and isobutylmagnesium chloride are preferred.

[0035] As the alkylmagnesium halide, for example, there can be mentioned methylmagnesium chloride (Mg(CH3)Cl), ethylmagnesium chloride (Mg(C2H5)Cl), propylmagnesium chloride (Mg(C3H7)Cl), n-butylmagnesium chloride (Mg(C4H9)Cl), isobutylmagnesium chloride (Mg(i-C4H9)Cl), methylmagnesium bromide (Mg(CH3)Br), ethylmagnesium bromide (Mg(C2H5)Br), propylmagnesium bromide (Mg(C3H7)Br), n-butylmagnesium bromide (Mg(C4H9)Br), isobutylmagnesium bromide (Mg(i-C4H9)Br), methylmagnesium iodide (Mg(CH3)I), ethylmagnesium iodide (Mg(C2H5)I), propylmagnesium iodide (Mg(C3H7)I), n-butylmagnesium iodide (Mg(C4H9)I), isobutylmagnesium iodide (Mg(i-C4H9)I), and the like, of which methylmagnesium chloride, ethylmagnesium chloride and isobutylmagnesium chloride are preferred.

[0036] As the alkylmagnesium halide, for example, there can be mentioned methylmagnesium chloride (Mg(CH3)Cl), ethylmagnesium chloride (Mg(C2H5)Cl), propylmagnesium chloride (Mg(C3H7)Cl), n-butylmagnesium chloride (Mg(C4H9)Cl), isobutylmagnesium chloride (Mg(i-C4H9)Cl), methylmagnesium bromide (Mg(CH3)Br), ethylmagnesium bromide (Mg(C2H5)Br), propylmagnesium bromide (Mg(C3H7)Br), n-butylmagnesium bromide (Mg(C4H9)Br), isobutylmagnesium bromide (Mg(i-C4H9)Br), methylmagnesium iodide (Mg(CH3)I), ethylmagnesium iodide (Mg(C2H5)I), propylmagnesium iodide (Mg(C3H7)I), n-butylmagnesium iodide (Mg(C4H9)I), isobutylmagnesium iodide (Mg(i-C4H9)I), and the like, of which methylmagnesium chloride, ethylmagnesium chloride and isobutylmagnesium chloride are preferred.

[0037] Examples of the alkyl alkoxymagnesium include methyl methoxymagnesium (Mg(OCH3)(CH3)), methyl ethoxymagnesium (Mg(OC2H5)(CH3)), methyl propoxymagnesium (Mg(OC3H7)(CH3)), methyl n-butoxymagnesium (Mg(OC4H9)(CH3)), methyl isobutoxymagnesium (Mg(i-OC4H9)(CH3)), ethyl methoxymagnesium (Mg(OCH3)(C2H5)), ethyl ethoxymagnesium (Mg(OC2H5)(C2H5)), ethyl propoxymagnesium (Mg(OC3H7)(C2H5)), ethyl n-butoxymagnesium (Mg(OC4H9)(C2H5)), ethyl isobutoxymagnesium (Mg(i-OC4H9)(C2H5)), propyl methoxymagnesium (Mg(OCH3)(C3H7)), propyl ethoxymagnesium (Mg(OC2H5)(C3H7)), propyl propoxymagnesium (Mg(OC3H7)(C3H7)), Propyl magnesium oxide (Mg(OC4H9)(C3H7)), propyl magnesium oxide (Mg(i-OC4H9)(C3H7)), n-butyl magnesium oxide (Mg(OCH3)(C4H9)), n-butyl magnesium oxide (Mg(OC2H5)(C4H9)), n-butyl magnesium oxide (Mg(OC3H7)(C4H9)), n-butyl magnesium oxide (Mg(OC4H9)(C4H9)), n-butyl magnesium oxide (Mg(OC4H9)(C4H9)), n-butyl magnesium oxide (Mg(OC4H9)(C4H9)), n-butyl magnesium oxide (Mg(i-OC4H9)(C3H7)), n-butyl magnesium oxide (Mg(OC4H9)(C4H9)), n-butyl magnesium oxide (Mg(i -OC4H9)(C4H9)), isobutyl methoxymagnesium (Mg(OCH3)(i-C4H9)), isobutyl ethoxymagnesium (Mg(OC2H5)(i-C4H9)), isobutyl propoxymagnesium (Mg(OC3H7)(i-C4H9)), isobutyl n-butoxymagnesium (Mg(OC4H9)(i-C4H9)) and isobutyl isobutoxymagnesium (Mg(i-OC4H9)(i-C4H9)), etc., among which butyl ethoxymagnesium is preferred.

[0038] These magnesium compounds may be used alone or in combination of two or more, and there is no particular limitation.

[0039] When used in a mixed form, the molar ratio between any two magnesium compounds in the magnesium compound mixture may be any ratio, for example, 0.25 to 4:1, preferably 0.5 to 3:1, and more preferably 1 to 2:1.

[0040] According to the present application, the term "non-metallocene complex" is a single-site olefin polymerization catalyst which does not contain a cyclopentadienyl ring, a fluorene ring or an indene ring or the like cyclopentadienyl group or its derivative in its structure and which is a metal organic compound capable of showing an olefin polymerization catalytic activity when combined with a cocatalyst (such as those described below) (and thus the non-metallocene complex is sometimes also referred to as a non-metallocene olefin polymerization complex). The compound contains a central metal atom and at least one polydentate ligand (preferably a tridentate ligand or more) which is bound to the central metal atom by a coordinate bond, and the term "non-metallocene ligand" is the aforementioned polydentate ligand.

[0041] According to the present application, the non-metallocene ligand is selected from the group consisting of compounds having the following chemical structural formula:

[0042]

[0043] According to the present application, the groups A, D and E (coordination groups) in the compound form a coordinate bond by a coordinate reaction with the IVB group metal atom contained in the IVB group metal compound used as a chemical treatment agent in the present application through the coordination atoms (such as N, O, S, Se and P or the like hetero atom) contained therein, thereby forming a complex (i.e. the non-metallocene complex according to the present application) having the IVB group metal atom as a central metal atom M.

[0044] In a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (A) and compounds (B) having the following chemical structural formula:

[0045]

[0046] In a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (A-1) to compounds (A-4) and compounds (B-1) to compounds (B-4) having the following chemical structural formula:

[0047]

[0048]

[0049] In all of the above chemical structural formulas,

[0050] q is 0 or 1;

[0051] d is 0 or 1;

[0052] A is selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, -NR 23 R 24 , -N(O)R 25 R 26 , -PR 28 R 29 , -P(O)R 30 OR 31 , sulfone, sulfoxide or -Se(O)R 39 wherein N, O, S, Se and P are each a coordinating atom;

[0053] B is selected from a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group or a C1-C 30 hydrocarbon group;

[0054] D is selected from a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C1-C 30 hydrocarbon group, a sulfone group or a sulfoxide group, wherein N, O, S, Se and P are each a coordinating atom;

[0055] 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;

[0056] 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;

[0057] G is selected from a C1-C 30 hydrocarbon group, a substituted C1-C 30 hydrocarbon group or an inert functional group;

[0058] 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;

[0059] 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), such as can be mentioned -NR 23 R 24 , -N(O)R 25 R 26 , -PR 28 R 29 , -P(O)R 30 R 31 , -OR 34 , -SR 35 , -S(O)R 36 , -SeR 38 or -Se(O)R 39 wherein N, O, S, Se and P are each a coordinating atom;

[0060] → represents a single bond or a double bond;

[0061] - represents a covalent bond or an ionic bond.

[0062] R 1 to R 4 , R 6 to R 21 are each independently selected from the group consisting of hydrogen, C1-C 30 alkyl, substituted C1-C 30 alkyl (wherein halogenated alkyl groups such as -CH2Cl and -CH2CH2Cl are preferred) or an inert functional group. R 22 to R 36 , R 38 and R 39 are each independently selected from the group consisting of hydrogen, C1-C 30 alkyl or substituted C1-C 30 alkyl (wherein halogenated alkyl groups such as -CH2Cl and -CH2CH2Cl are preferred). The above groups can be the same as or different from each other, wherein adjacent groups such as R 1 and R 2 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 18 and R 19 , R 19 and R 20 , R 20 and R 21 , R 23 and R 24 , or R 25 and R 26 may be bonded together to form a bond or a ring, preferably an aromatic ring, such as an unsubstituted benzene ring or a benzene ring substituted with 1 to 4 C1-C 30 alkyl or substituted C1-C 30 alkyl (wherein halogenated alkyl groups such as -CH2Cl and -CH2CH2Cl are preferred).

[0063] R 5 is selected from the group consisting of a lone pair of electrons on nitrogen, hydrogen, C1-C 30 alkyl, substituted C1-C 30 alkyl, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group. When R 5 is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R 5N, O, S, P and Se in the above formulae can act as coordinating atoms (coordinating to the central metal atom M).

[0064] In the context of the present application, the inert functional groups can be mentioned, for example, selected from halogen, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C1-C 10 C1-C 30 alkyl groups and substituted C1-C 30 alkyl groups.

[0065] In the context of the present application, the inert functional groups have the following characteristics, limited by the chemical structure of the multidentate ligand according to the present application:

[0066] (1) do not interfere with the coordination process of the groups A, D, E, F, Y or Z to the central metal atom M, and

[0067] (2) have a lower coordinating ability to the central metal atom M than the A, D, E, F, Y and Z groups, and do not displace the existing coordination of these groups to the central metal atom M.

[0068] According to the present application, in all of the above chemical formulae, any two or more adjacent groups, such as R 21 to group Z, or R 13 to group Y, can be combined together to form a ring, preferably a C6-C 30 aromatic heterocycle, such as a pyridine ring, etc., wherein the aromatic heterocycle is optionally substituted with 1 or more substituents selected from C1-C 30 alkyl groups and substituted C1-C 30 alkyl groups.

[0069] In the context of the present application, the halogen is selected from F, Cl, Br or I. The nitrogen-containing group is selected from -NR 23 R 24 , -T-NR 23 R 24 or -N(O)R 25 R 26 . The phosphorus-containing group is selected from -PR 28 R 29 , -P(O)R 30 R 31 or -P(O)R 32 (OR 33 ). The oxygen-containing group is selected from hydroxyl, -OR 34 and -T-OR34 The sulfur-containing group is selected from -SR 35 , -T-SR 35 , -S(O)R 36 or -T-SO2R 37 The selenium-containing group is selected from -SeR 38 , -T-SeR 38 , -Se(O)R 39 or -T-Se(O)R 39 The group T is selected from C1-C 30 hydrocarbyl or substituted C1-C 30 hydrocarbyl. The R 37 group is selected from hydrogen, C1-C 30 hydrocarbyl or substituted C1-C 30 hydrocarbyl.

[0070] In the context of the present application, the C1-C 30 hydrocarbyl group is selected from C1-C 30 alkyl (preferably C1-C6alkyl, such as isobutyl), C7-C 30 alkylaryl (such as tolyl, xylyl, diisobutylphenyl, etc.), C7-C 30 aralkyl (such as benzyl), C3-C 30 cycloalkyl, C2-C 30 alkenyl, C2-C 30 alkynyl, C6-C 30 aryl (such as phenyl, naphthyl, anthryl, etc.), C8-C 30 fused ring group or C4-C 30 heterocyclic group, wherein the heterocyclic group contains 1 to 3 heteroatoms selected from nitrogen, oxygen or sulfur atoms, such as pyridyl, pyrrolyl, furanyl or thienyl, etc.

[0071] According to the present application, in the context of the present application, the C1-C 30 hydrocarbyl group sometimes refers to a C1-C 30 hydrocarbyldiyl group (divalent group, or alternatively C1-C 30 hydrocarbylene group) or a C1-C 30 hydrocarbyltriiyl group (trivalent group), as will be apparent to the skilled person.

[0072] In the context of the present application, the substituted C1-C 30 hydrocarbyl group refers to a C1-C 30 hydrocarbyl group bearing one or more inert substituents. By inert substituents, it is meant that these substituents are inert with respect to the aforementioned coordinating group (referring to the aforementioned groups A, D, E, F, Y and Z, or optionally also R 5) does not substantially interfere with the coordination process of the central metal atom M (i.e., the aforementioned Group IVB metal atom); in other words, due to the chemical structure of the ligand of the present invention, these substituents have no ability or opportunity (for example, due to steric hindrance, etc.) to react with the Group IVB metal atom to form a coordination bond. Generally speaking, the inert substituent is selected from halogen or C1-C 30 Alkyl (preferably C1-C6 alkyl, such as isobutyl).

[0073] In the context of the present invention, the silicon-containing group is selected from -SiR 42 R 43 R 44 or-T-SiR 45 ; The germanium-containing group is selected from -GeR 46 R 47 R 48 or-T-GeR 49 ; The tin-containing group is selected from -SnR 50 R 51 R 52 、-T-SnR 53 or -T-Sn(O)R 54 ; and said R 42 to R 54 Each independently selected from hydrogen, the aforementioned C1-C 30 Hydrocarbon or the aforementioned substituted C1-C 30 The hydrocarbon groups may be the same or different from each other, and adjacent groups may be combined to form a bond or a ring. The group T is as defined above.

[0074] As the non-metallocene ligand, for example, the following compounds can be mentioned:

[0075]

[0076]

[0077]

[0078]

[0079] The non-metallocene ligand is preferably selected from the following compounds:

[0080]

[0081]

[0082] The non-metallocene ligand is further preferably selected from the following compounds:

[0083]

[0084] The non-metallocene ligand is more preferably selected from the group consisting of the following compounds:

[0085]

[0086] These non-metallocene ligands can be used singly or in combination in any ratio.

[0087] According to the present application, the non-metallocene ligand is not a diether compound which is generally used as an electron donor compound in the art.

[0088] The non-metallocene ligand can be manufactured by any method known to those skilled in the art. For the details of the manufacturing method thereof, see, for example, WO 03 / 010207 and Chinese Patents ZL01126323.7 and ZL02110844.7, etc., the entire contents of which are incorporated herein by reference.

[0089] According to the present application, the term "alcohol" means a compound obtained by substituting at least one hydrogen atom on a hydrocarbon chain (such as C 1-30 hydrocarbon) with a hydroxyl group. It can be one or more selected from the group consisting of aliphatic alcohol, aromatic alcohol and alicyclic alcohol.

[0090] As the alcohol, for example, there can be mentioned C 1-30 aliphatic alcohol (preferably C 1-30 aliphatic monohydric alcohol), C 6-30 aromatic alcohol (preferably C 6-30 aromatic monohydric alcohol) and C 4-30 alicyclic alcohol (preferably C 4-30 alicyclic monohydric alcohol), of which C 1-30 aliphatic monohydric alcohol or C 2-8 aliphatic monohydric alcohol, more preferably ethanol and butanol. In addition, the alcohol can be optionally substituted with a substituent selected from a halogen atom or C 1-6 alkoxy group.

[0091] As the C 1-30 aliphatic alcohol, for example, there can be mentioned methanol, ethanol, propanol, 2-propanol, butanol, pentanol, 2-methylpentanol, 2-ethylpentanol, 2-hexylbutanol, hexanol and 2-ethylhexanol, etc., of which ethanol, propanol, butanol and 2-ethylhexanol are preferred.

[0092] As the C 6-30 aromatic alcohol, for example, there can be mentioned benzyl alcohol, phenethyl alcohol and methylbenzyl alcohol, etc., of which phenethyl alcohol is preferred.

[0093] As the C 4-30Alicyclic alcohols, such as, for example, cyclohexanol, cyclopentanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, methylcyclooctanol, ethylcyclooctanol, propylcyclooctanol, and the like, of which cyclohexanol and methylcyclohexanol are preferred.

[0094] As the alcohol substituted with a halogen atom, such as, for example, trichloromethanol, trichloroethanol, and trichlorohexanol, of which trichloromethanol is preferred.

[0095] As the alcohol substituted with an alkoxy group, such as, for example, ethylene glycol-ethyl ether, ethylene glycol-n-butyl ether, and 1-butoxy-2-propanol, of which ethylene glycol-ethyl ether is preferred.

[0096] These alcohols can be used singly or in a mixture of two or more. When used in a mixture of two or more, the ratio between any two of the alcohols in the alcohol mixture can be arbitrarily determined and is not particularly limited.

[0097] According to the present application, the alcohol is preferably one or more selected from the group consisting of aliphatic alcohols, more preferably one or more selected from the group consisting of ethanol, propanol, and butanol.

[0098] According to the present application, as the dilution solvent, one or more selected from the group consisting of alkanes and aromatic hydrocarbons. Of these, the alkanes are selected from the group consisting of paraffins, cycloparaffins, halogenated paraffins, and halogenated cycloparaffins.

[0099] As the paraffin, such as, for example, pentane, hexane, heptane, octane, nonane, and decane, of which hexane, heptane, and decane are preferred, most preferably hexane and decane.

[0100] As the cycloparaffin, such as, for example, cyclohexane, cyclopentane, cycloheptane, cyclodecane, and cyclononane, most preferably cyclohexane.

[0101] As the halogenated paraffin, such as, for example, dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, and tribromobutane, and the like.

[0102] As the halogenated cycloparaffin, such as, for example, chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane, and the like.

[0103] As the aromatic hydrocarbon, one or more selected from the group consisting of C 6-12 As the halogenated C 6-12 As the aromatic hydrocarbon, one or more selected from the group consisting of C 6-12 As the aromatic hydrocarbon, one or more selected from the group consisting of C

[0104] These dilution solvents may be used alone or in combination of two or more in any proportion.

[0105] When preparing the magnesium support, the molar ratio of the magnesium compound to the non-metallocene ligand, calculated as Mg element, is 1:0.01-0.20, preferably 1:0.03-0.15. The molar ratio of the magnesium compound to the alcohol, calculated as Mg element, is 1:10-50, preferably 1:15-30. The amount of the dilution solvent is generally calculated by volume, with the ratio of the magnesium compound to the dilution solvent being 1 mol:0.5-4 L, preferably 1 mol:1-3 L.

[0106] The magnesium compound and non-metallocene ligand are dissolved in the alcohol, typically under stirring to facilitate dissolution. This stirring can be accomplished using any means, such as a stirring paddle (typically at a speed of 10 to 1000 rpm). If desired, dissolution can be facilitated by appropriate heating, such as at a temperature from 40°C to 5°C below the boiling point of the alcohol.

[0107] In one embodiment of the present invention, the magnesium compound and the non-metallocene ligand are completely dissolved in alcohol. In one embodiment of the present invention, a diluent solvent is added to the alcohol solution of the magnesium compound and the non-metallocene ligand, mixed to form a uniform solution, and then dried to obtain a magnesium support.

[0108] The dilution solvent can be added in one go or dropwise, preferably in one go. As one of the mixing methods, stirring can be used to promote the dispersion of the dilution solvent in the solution. The stirring can be in any form, such as a stirring paddle (usually with a rotation speed of 10 to 1000 rpm).

[0109] There is no particular limitation on the temperature of the dilution solvent. To avoid large fluctuations in the solution temperature, the solvent temperature is generally selected to be the dissolution temperature of the magnesium compound and the non-metallocene ligand in the alcohol.

[0110] After adding a diluting solvent and mixing, the obtained magnesium compound solution is dried to remove part of the alcohol therein, thereby obtaining the magnesium carrier.

[0111] According to the present invention, the magnesium compound solution is dried so that the weight ratio of the alcohol content in the magnesium support relative to the magnesium support is 1.0-3.0 wt %, preferably 1.1-2.5 wt %, more preferably 1.5-2.0 wt %.

[0112] According to the present invention, the drying can be carried out by conventional methods, such as inert gas drying, vacuum drying or heating drying under vacuum, preferably inert gas drying or heating drying under vacuum, most preferably heating drying under vacuum.

[0113] According to the present application, the drying method (including drying temperature, drying vacuum, and drying time) is not limited as long as the alcohol content of the magnesium carrier satisfies the aforementioned requirements of the present application. For example, the magnesium compound solution is dried at a temperature of 5 to 50°C lower than the boiling point of the dilution solvent, preferably at a temperature of 10 to 30°C lower than the boiling point of the dilution solvent, under a vacuum of 2 to 100 mBar of absolute pressure, preferably under a vacuum of 5 to 50 mBar of absolute pressure, for 2 to 30 h, preferably for 4 to 12 h, thereby obtaining the magnesium carrier.

[0114] The steps for obtaining the magnesium-aluminum carrier are described in detail below.

[0115] The method for producing the magnesium carrier-supported non-metallocene catalyst of the present application includes the steps of adding an alkyl aluminum to a magnesium carrier to react, and filtering to obtain a magnesium-aluminum carrier.

[0116] According to the present application, as the alkyl aluminum, for example, a compound represented by the following general formula (I) can be mentioned:

[0117] Al(R)3 (I)

[0118] wherein the groups R are the same as or different from each other (preferably the same), and each is independently selected from the group consisting of C1-C8 alkyl groups, preferably methyl, ethyl, and isobutyl, most preferably methyl.

[0119] Specifically, as the alkyl aluminum, for example, trimethyl aluminum (Al(CH3)3), triethyl aluminum (Al(CH3CH2)3), tripropyl aluminum (Al(C3H7)3), triisobutyl aluminum (Al(i-C4H9)3), tri-n-butyl aluminum (Al(C4H9)3), triisopentyl aluminum (Al(i-C5H 11 )3), tri-n-pentyl aluminum (Al(C5H 11 )3), tri-n-hexyl aluminum (Al(C6H 13 )3), triisohexyl aluminum (Al(i-C6H 13 )3), diethylmethyl aluminum (Al(CH3)(CH3CH2)2), and dimethylethyl aluminum (Al(CH3CH2)(CH3)2), and the like can be mentioned, of which trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, and tri-n-hexyl aluminum are preferred, and triethyl aluminum and triisobutyl aluminum are most preferred.

[0120] These alkyl aluminums can be used singly or in combination of a plurality of kinds in any ratio.

[0121] According to the present application, the addition of the alkyl aluminum to the magnesium carrier can be performed in the presence of an alkane solvent or without the need for an alkane solvent, and is preferably performed in the presence of an alkane solvent. The alkane solvent used herein can be the same as or different from the alkane solvent in the aforementioned dilution solvent.

[0122] Specifically, as the alkane solvent, for example, C 5-12 Alkanes, C 5-12 Cycloalkanes, halogenated C 5-12 Alkanes, halogenated C 5-12 Examples of cycloalkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, and chlorocyclohexane. Among these, pentane, hexane, decane, and cyclohexane are preferred, and hexane is most preferred. These solvents may be used alone or in combination of multiple types in any ratio.

[0123] In one embodiment of the present invention, as a method for preparing a magnesium-aluminum support, an alkane solvent is first optionally added to a magnesium support, and then the alkyl aluminum is metered (preferably slowly added dropwise) under stirring conditions to form a reaction mixture. In one embodiment of the present invention, in order to avoid excessive reaction and protect the structure of the magnesium support, it is generally necessary to first react at room temperature for a longer time, such as 0.5-12 hours, preferably 2-8 hours, and then heat to 60°C to 100°C for a shorter reaction time, such as 0.25-2 hours, preferably 0.5-1 hour. In one embodiment of the present invention, the reaction progress can also be controlled by gradient heating and insulation. Generally, the reaction is first carried out at room temperature for 0.25-4 hours, preferably 0.5-2 hours, then the temperature is raised to 40°C for reaction for 0.25-2 hours, preferably 0.5-1 hours, then the temperature is raised to 60°C for reaction for 0.25-2 hours, preferably 0.5-1 hours, and then the temperature is raised to 80°C for reaction for 0.25-2 hours, preferably 0.5-1 hours, wherein the heating rate is generally 10-60°C / h. Preferably, the reaction progress is controlled by gradient heating and insulation.

[0124] In one embodiment of the present invention, the obtained reaction mixture is filtered, optionally washed (1 to 6 times, preferably 1 to 3 times), and optionally dried to obtain a magnesium aluminum support. In one embodiment of the present invention, drying is not required. Preferably, drying is not required. The washing solvent may be the same alkane solvent as described above in the present invention, or a different alkane solvent may be selected, preferably decane and hexane, and most preferably hexane.

[0125] According to the present invention, the amount of the alkyl aluminum used is such that the molar ratio of the magnesium compound calculated as Mg element to the alkyl aluminum calculated as aluminum element is 1:0.5-5, preferably 1:1-3.

[0126] The steps of treating with a chemical treatment agent are described in detail below.

[0127] The method for preparing the magnesium carrier-supported non-metallocene catalyst of the present application comprises: treating the magnesium-aluminum carrier with a chemical treating agent selected from a group IVB metal compound at -40 to 10°C, preferably -20 to 0°C to obtain the magnesium carrier-supported non-metallocene catalyst.

[0128] According to the present application, by chemically treating the magnesium-aluminum carrier with the chemical treating agent, the chemical treating agent can react with the non-metallocene ligand contained in the magnesium-aluminum carrier, thereby generating a non-metallocene complex in situ on the carrier (in-situ loading reaction), thus obtaining the supported non-metallocene catalyst of the present application.

[0129] According to the present application, a group IVB metal compound is used as the chemical treating agent.

[0130] As the group IVB metal compound, for example, a group IVB metal halide, a group IVB metal alkyl compound, a group IVB metal alkoxy compound, a group IVB metal alkyl halide and a group IVB metal alkoxy halide can be mentioned.

[0131] As the group IVB metal halide, the group IVB metal alkyl compound, the group IVB metal alkoxy compound, the group IVB metal alkyl halide and the group IVB metal alkoxy halide, for example, a compound having the following general formula (II) structure can be mentioned:

[0132] M(OR 1 ) m X n R 2 4-m-n (II)

[0133] In formula (II):

[0134] m is 0, 1, 2, 3 or 4;

[0135] n is 0, 1, 2, 3 or 4;

[0136] M is a group IVB metal in the periodic table, such as titanium, zirconium and hafnium, etc.

[0137] X is a halogen, such as F, Cl, Br and I; and

[0138] R 1 and R 2 are each independently selected from C 1-10 alkyl, such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R 1 and R 2 may be the same or different.

[0139] Specifically, as the Group IVB metal halide, for example, titanium tetrafluoride (TiF4), titanium tetrachloride (TiCl4), titanium tetrabromide (TiBr4), titanium tetraiodide (TiI4) can be mentioned;

[0140] zirconium tetrafluoride (ZrF4), zirconium tetrachloride (ZrCl4), zirconium tetrabromide (ZrBr4), zirconium tetraiodide (ZrI4);

[0141] hafnium tetrafluoride (HfF4), hafnium tetrachloride (HfCl4), hafnium tetrabromide (HfBr4), hafnium tetraiodide (HfI4).

[0142] As the Group IVB metal alkyl compound, for example, titanium tetramethyl (Ti(CH3)4), titanium tetraethyl (Ti(CH3CH2)4), titanium tetraisobutyl (Ti(i-C4H9)4), titanium tetra-n-butyl (Ti(C4H9)4), titanium trimethylmethyl (Ti(CH3)(CH3CH2)3), titanium dimethyldiethyl (Ti(CH3)2(CH3CH2)2), titanium trimethylethyl (Ti(CH3)3(CH3CH2)), titanium triisobutylmethyl (Ti(CH3)(i-C4H9)3), titanium diisobutyldimethyl (Ti(CH3)2(i-C4H9)2), titanium trimethylisobutyl (Ti(CH3)3(i-C4H9)), titanium triisobutylethyl (Ti(CH3CH2)(i-C4H9)3), titanium diisobutyldiethyl (Ti(CH3CH2)2(i-C4H9)2), titanium triethylisobutyl (Ti(CH3CH2)3(i-C4H9)), titanium tri-n-butylmethyl (Ti(CH3)(C4H9)3), titanium di-n-butyldimethyl (Ti(CH3)2(C4H9)2), titanium trimethyl-n-butyl (Ti(CH3)3(C4H9)), titanium tri-n-butyethyl (Ti(CH3CH2)(C4H9)3), titanium di-n-butydiethyl (Ti(CH3CH2)2(C4H9)2), titanium triethyl-n-butyl (Ti(CH3CH2)3(C4H9)), and the like can be mentioned;

[0143] tetraethylzirconium (Zr(CH3CH2)4), tetraisobutylzirconium (Zr(i-C4H9)4), tetra-n- butylzirconium (Zr(C4H9)4), triethylmethylzirconium (Zr(CH3)(CH3CH2)3), diethyldimethylzirconium (Zr(CH3)2(CH3CH2)2), trimethylethylzirconium (Zr(CH3)3(CH3CH2)), triisobutylmethylzirconium (Zr(CH3)(i-C4H9)3), diisobutyldimethylzirconium (Zr(CH3)2(i-C4H9)2), trimethylisobutylzirconium (Zr(CH3)3(i-C4H9)), triisobutylethylzirconium (Zr(CH3CH2)(i-C4H9)3), diisobutyldiethylzirconium (Zr(CH3CH2)2(i-C4H9)2), triethylisobutylzirconium (Zr(CH3CH2)3(i-C4H9)), tri-n- butylmethylzirconium (Zr(CH3)(C4H9)3), di-n-butyldimethylzirconium (Zr(CH3)2(C4H9)2), trimethyl-n-butyhzirconium (Zr(CH3)3(C4H9)), tri-n-butyiethylzirconium (Zr(CH3CH2)(C4H9)3), di-n-butyldiethylzirconium (Zr(CH3CH2)2(C4H9)2), triethyl-n-butyhzirconium (Zr(CH3CH2)3(C4H9)), and the like;

[0144] tetraethylhafnium (Hf(CH3CH2)4), tetraisobutylhafnium (Hf(i-C4H9)4), tetra-n- butylhafnium (Hf(C4H9)4), triethylmethylhafnium (Hf(CH3)(CH3CH2)3), diethyldimethylhafnium (Hf(CH3)2(CH3CH2)2), trimethylethylhafnium (Hf(CH3)3(CH3CH2)), triisobutylmethylhafnium (Hf(CH3)(i-C4H9)3), diisobutyldimethylhafnium (Hf(CH3)2(i-C4H9)2), trimethylisobutylhafnium (Hf(CH3)3(i-C4H9)), triisobutylethylhafnium (Hf(CH3CH2)(i-C4H9)3), diisobutyldiethylhafnium (Hf(CH3CH2)2(i-C4H9)2), triethylisobutylhafnium (Hf(CH3CH2)3(i-C4H9)), tri-n- butylmethylhafnium (Hf(CH3)(C4H9)3), di-n-butyldimethylhafnium (Hf(CH3)2(C4H9)2), trimethyl-n-butyhzirconium (Hf(CH3)3(C4H9)), tri-n-butyiethylhafnium (Hf(CH3CH2)(C4H9)3), di-n-butyldiethylhafnium (Hf(CH3CH2)2(C4H9)2), triethyl-n-butyhzirconium (Hf(CH3CH2)3(C4H9)), and the like.

[0145] As the Group IVB metal alkoxide compounds, for example, tetramethoxytitanium (Ti(OCH3)4), tetraethoxytitanium (Ti(OCH3CH2)4), tetraisobutyloxytitanium (Ti(i-OC4H9)4), tetra-n-butyloxytitanium (Ti(OC4H9)4), triethoxymethoxytitanium (Ti(OCH3)(OCH3CH2)3), diethoxydimethoxytitanium (Ti(OCH3)2(OCH3CH2)2), trimethoxyethoxytitanium (Ti(OCH3)3(OCH3CH2)), triisobutyloxymethoxytitanium (Ti(OCH3)(i-OC4H9)3), diisobutyloxydimethoxytitanium (Ti(OCH3)2(i-OC4H9)2), trimethoxyisobutyloxytitanium (Ti(OCH3)3(i-OC4H9)), triisobutyloxyethoxytitanium (Ti(OCH3CH2)(i-OC4H9)3), diisobutyloxydiethoxytitanium (Ti(OCH3CH2)2(i-OC4H9)2), triethoxyisobutyloxytitanium (Ti(OCH3CH2)3(i-OC4H9)), tri-n-butyloxymethoxytitanium (Ti(OCH3)(OC4H9)3), di-n-butyloxydimethoxytitanium (Ti(OCH3)2(OC4H9)2), trimethoxy-n-butyloxytitanium (Ti(OCH3)3(OC4H9)), tri-n-butyloxyethoxytitanium (Ti(OCH3CH2)(OC4H9)3), di-n-butyloxydiethoxytitanium (Ti(OCH3CH2)2(OC4H9)2), triethoxy-n-butyloxytitanium (Ti(OCH3CH2)3(OC4H9)), and the like can be given.

[0146] tetraethoxysilane (Si(OCH2CH3)4), tetraisobutoxysilane (Si(i-OC4H9)4), tetra-n-butoxysilane (Si(OC4H9)4), triethoxymethoxysilane (Si(OCH3)(OCH2CH3)3), diethoxydimethoxysilane (Si(OCH3)2(OCH2CH2)2), tri-methoxyethoxysilane (Si(OCH3)3(OCH2CH2)), triisobutoxymethoxysilane (Si(OCH3)(i-OC4H9)3), diisobutoxydimethoxysilane (Si(OCH3)2(i-OC4H9)2), tri-methoxyisobutoxysilane (Si(OCH3)3(i-C4H9)), triisobutoxyethoxysilane (Si(OCH2CH2)(i-OC4H9)3), diisobutoxydiethoxysilane (Si(OCH2CH2)2(i-OC4H9)2), tri-ethoxyisobutoxysilane (Si(OCH2CH2)3(i-OC4H9)), tri-n-butoxymethoxysilane (Si(OCH3)(OC4H9)3), di-n-butoxydimethoxysilane (Si(OCH3)2(OC4H9)2), tri-methoxy-n-butoxysilane (Si(OCH3)3(OC4H9)), tri-n-butoxyethoxysilane (Si(OCH2CH2)(OC4H9)3), di-n-butoxydiethoxysilane (Si(OCH2CH2)2(OC4H9)2), tri-ethoxy-n-butoxysilane (Si(OCH2CH2)3(OC4H9)), and the like;

[0147] tetraethoxyhafnium (Hf(OCH3CH2)4), tetraisobutoxyhafnium (Hf(i-OC4H9)4), tetra-n-butoxyhafnium (Hf(OC4H9)4), triethoxymethoxyhafnium (Hf(OCH3)(OCH3CH2)3), diethoxydimethoxyhafnium (Hf(OCH3)2(OCH3CH2)2), trimethoxyethoxyhafnium (Hf(OCH3)3(OCH3CH2)), triisobutoxymethoxyhafnium (Hf(OCH3)(i-OC4H9)3), diisobutoxydimethoxyhafnium (Hf(OCH3)2(i-OC4H9)2), triisobutoxyethoxyhafnium (Hf(OCH3CH2)(i-OC4H9)3), diisobutoxydiethoxyhafnium (Hf(OCH3CH2)2(i-OC4H9)2), triethoxyisobutoxyhafnium (Hf(OCH3CH2)3(i-C4H9)), tri-n-butoxymethoxyhafnium (Hf(OCH3)(OC4H9)3), di-n-butoxydimethoxyhafnium (Hf(OCH3)2(OC4H9)2), tri-n-butoxyethoxyhafnium (Hf(OCH3)3(OC4H9)), and the like.

[0148] As the Group IVB metal alkyl halide, for example, there can be mentioned trimethyl titanium chloride (TiCl(CH3)3), triethyl titanium chloride (TiCl(CH3CH2)3), triisobutyl titanium chloride (TiCl(i-C4H9)3), tri-n-butyl titanium chloride (TiCl(C4H9)3), dimethyl titanium dichloride (TiCl2(CH3)2), diethyl titanium dichloride (TiCl2(CH3CH2)2), diisobutyl titanium dichloride (TiCl2(i-C4H9)2), tri-n-butyl titanium chloride (TiCl(C4H9)3), methyl titanium trichloride (Ti(CH3)Cl3), ethyl titanium trichloride (Ti(CH3CH2)Cl3), isobutyl titanium trichloride (Ti(i-C4H9)Cl3), n-butyl titanium trichloride (Ti(C4H9)Cl3);

[0149] trimethyl titanium bromide (TiBr(CH3)3), triethyl titanium bromide (TiBr(CH3CH2)3), triisobutyl titanium bromide (TiBr(i-C4H9)3), tri-n-butyl titanium bromide (TiBr(C4H9)3), dimethyl titanium dibromide (TiBr2(CH3)2), diethyl titanium dibromide (TiBr2(CH3CH2)2), diisobutyl titanium dibromide (TiBr2(i-C4H9)2), tri-n-butyl titanium bromide (TiBr(C4H9)3), methyl titanium tribromide (Ti(CH3)Br3), ethyl titanium tribromide (Ti(CH3CH2)Br3), isobutyl titanium tribromide (Ti(i-C4H9)Br3), n-butyl titanium tribromide (Ti(C4H9)Br3);

[0150] trimethyl zirconium chloride (ZrCl(CH3)3), triethyl zirconium chloride (ZrCl(CH3CH2)3), triisobutyl zirconium chloride (ZrCl(i-C4H9)3), tri-n-butyl zirconium chloride (ZrCl(C4H9)3), dimethyl zirconium dichloride (ZrCl2(CH3)2), diethyl zirconium dichloride (ZrCl2(CH3CH2)2), diisobutyl zirconium dichloride (ZrCl2(i-C4H9)2), tri-n-butyl zirconium chloride (ZrCl(C4H9)3), methyl zirconium trichloride (Zr(CH3)Cl3), ethyl zirconium trichloride (Zr(CH3CH2)Cl3), isobutyl zirconium trichloride (Zr(i-C4H9)Cl3), n-butyl zirconium trichloride (Zr(C4H9)Cl3);

[0151] trimethyl zirconium bromide (ZrBr(CH3)3), triethyl zirconium bromide (ZrBr(CH3CH2)3), triisobutyl zirconium bromide (ZrBr(i-C4H9)3), tri-n-butyl zirconium bromide (ZrBr(C4H9)3), dimethyl zirconium dibromide (ZrBr2(CH3)2), diethyl zirconium dibromide (ZrBr2(CH3CH2)2), diisobutyl zirconium dibromide (ZrBr2(i-C4H9)2), tri-n-butyl zirconium bromide (ZrBr(C4H9)3), methyl zirconium tribromide (Zr(CH3)Br3), ethyl zirconium tribromide (Zr(CH3CH2)Br3), isobutyl zirconium tribromide (Zr(i-C4H9)Br3), n-butyl zirconium tribromide (Zr(C4H9)Br3);

[0152] trimethylhafnium chloride (HfCI(CH3)3), triethylhafnium chloride (HfCI(CH3CH2)3), triisobutylhafnium chloride (HfCI(i-C4H9)3), tri-n-butylhafnium chloride (HfCI(C4H9)3), dimethylhafnium dichloride (HfCI2(CH3)2), diethylhafnium dichloride (HfCI2(CH3CH2)2), diisobutylhafnium dichloride (HfCI2(i-C4H9)2), tri-n-butylhafnium chloride (HfCI(C4H9)3), methylhafnium trichloride (Hf(CH3)CI3), ethylhafnium trichloride (Hf(CH3CH2)CI3), isobutylhafnium trichloride (Hf(i-C4H9)CI3), n-butylhafnium trichloride (Hf(C4H9)CI3);

[0153] trimethylhafnium bromide (HfBr(CH3)3), triethylhafnium bromide (HfBr(CH3CH2)3), triisobutylhafnium bromide (HfBr(i-C4H9)3), tri-n-butylhafnium bromide (HfBr(C4H9)3), dimethylhafnium dibromide (HfBr2(CH3)2), diethylhafnium dibromide (HfBr2(CH3CH2)2), diisobutylhafnium dibromide (HfBr2(i-C4H9)2), tri-n-butylhafnium bromide (HfBr(C4H9)3), methylhafnium tribromide (Hf(CH3)Br3), ethylhafnium tribromide (Hf(CH3CH2)Br3), isobutylhafnium tribromide (Hf(i-C4H9)Br3), n-butylhafnium tribromide (Hf(C4H9)Br3).

[0154] trimethoxyhafnium chloride (HfCI(OCH3)3), triethoxyhafnium chloride (HfCI(OCH3CH2)3), triisobutoxyhafnium chloride (HfCI(i-OC4H9)3), tri-n-butoxyhafnium chloride (HfCI(OC4H9)3), dimethoxyhafnium dichloride (HfCI2(OCH3)2), diethoxyhafnium dichloride (HfCI2(OCH3CH2)2), diisobutoxyhafnium dichloride (HfCI2(i-OC4H9)2), tri-n-butoxyhafnium chloride (HfCI(OC4H9)3), methoxyhafnium trichloride (Hf(OCH3)CI3), ethoxyhafnium trichloride (Hf(OCH3CH2)CI3), isobutoxyhafnium trichloride (Hf(i-C4H9)CI3), n-butoxyhafnium trichloride (Hf(OC4H9)CI3);

[0155] trimethoxy titanium bromide (TiBr(OCH3)3), triethoxy titanium bromide (TiBr(OCH3CH2)3), triisobutoxy titanium bromide (TiBr(i-OC4H9)3), tri-n-butoxy titanium bromide (TiBr(OC4H9)3), dimethoxy titanium dibromide (TiBr2(OCH3)2), diethoxy titanium dibromide (TiBr2(OCH3CH2)2), diisobutoxy titanium dibromide (TiBr2(i-OC4H9)2), tri-n-butoxy titanium bromide (TiBr(OC4H9)3), methoxy titanium tribromide (Ti(OCH3)Br3), ethoxy titanium tribromide (Ti(OCH3CH2)Br3), isobutoxy titanium tribromide (Ti(i-C4H9)Br3), n-butoxy titanium tribromide (Ti(OC4H9)Br3);

[0156] trimethoxy zirconium chloride (ZrCl(OCH3)3), triethoxy zirconium chloride (ZrCl(OCH3CH2)3), triisobutoxy zirconium chloride (ZrCl(i-OC4H9)3), tri-n-butoxy zirconium chloride (ZrCl(OC4H9)3), dimethoxy zirconium dichloride (ZrCl2(OCH3)2), diethoxy zirconium dichloride (ZrCl2(OCH3CH2)2), diisobutoxy zirconium dichloride (ZrCl2(i-OC4H9)2), tri-n-butoxy zirconium chloride (ZrCl(OC4H9)3), methoxy zirconium trichloride (Zr(OCH3)Cl3), ethoxy zirconium trichloride (Zr(OCH3CH2)Cl3), isobutoxy zirconium trichloride (Zr(i-C4H9)Cl3), n-butoxy zirconium trichloride (Zr(OC4H9)Cl3);

[0157] trimethoxy zirconium bromide (ZrBr(OCH3)3), triethoxy zirconium bromide (ZrBr(OCH3CH2)3), triisobutoxy zirconium bromide (ZrBr(i-OC4H9)3), tri-n-butoxy zirconium bromide (ZrBr(OC4H9)3), dimethoxy zirconium dibromide (ZrBr2(OCH3)2), diethoxy zirconium dibromide (ZrBr2(OCH3CH2)2), diisobutoxy zirconium dibromide (ZrBr2(i-OC4H9)2), tri-n-butoxy zirconium bromide (ZrBr(OC4H9)3), methoxy zirconium tribromide (Zr(OCH3)Br3), ethoxy zirconium tribromide (Zr(OCH3CH2)Br3), isobutoxy zirconium tribromide (Zr(i-C4H9)Br3), n-butoxy zirconium tribromide (Zr(OC4H9)Br3);

[0158] trimethoxyhafnium chloride (HfCl(OCH3)3), triethoxyhafnium chloride (HfCl(OCH3CH2)3), triisobutoxyhafnium chloride (HfCl(i-OC4H9)3), tri-n-butoxyhafnium chloride (HfCl(OC4H9)3), dimethoxyhafnium dichloride (HfCl2(OCH3)2), diethoxyhafnium dichloride (HfCl2(OCH3CH2)2), diisobutoxyhafnium dichloride (HfCl2(i-OC4H9)2), tri-n-butoxyhafnium chloride (HfCl(OC4H9)3), methoxyhafnium trichloride (Hf(OCH3)Cl3), ethoxyhafnium trichloride (Hf(OCH3CH2)Cl3), isobutoxyhafnium trichloride (Hf(i-C4H9)Cl3), n-butoxyhafnium trichloride (Hf(OC4H9)Cl3);

[0159] trimethoxyhafnium bromide (HfBr(OCH3)3), triethoxyhafnium bromide (HfBr(OCH3CH2)3), triisobutoxyhafnium bromide (HfBr(i-OC4H9)3), tri-n-butoxyhafnium bromide (HfBr(OC4H9)3), dimethoxyhafnium dibromide (HfBr2(OCH3)2), diethoxyhafnium dibromide (HfBr2(OCH3CH2)2), diisobutoxyhafnium dibromide (HfBr2(i-OC4H9)2), tri-n-butoxyhafnium bromide (HfBr(OC4H9)3), methoxyhafnium tribromide (Hf(OCH3)Br3), ethoxyhafnium tribromide (Hf(OCH3CH2)Br3), isobutoxyhafnium tribromide (Hf(i-C4H9)Br3), n-butoxyhafnium tribromide (Hf(OC4H9)Br3).

[0160] As the Group IVB metal compound, the Group IVB metal halide is preferred, and TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4and HfBr4are more preferred, and TiCl4and ZrCl4are most preferred.

[0161] These Group IVB metal compounds can be used singly or in combination of a plurality of kinds in any ratio.

[0162] When the chemical treatment agent is liquid at ordinary temperature, the chemical treatment reaction can be carried out directly using the chemical treatment agent. When the chemical treatment agent is solid at ordinary temperature, the chemical treatment agent is preferably used in the form of a solution for the sake of ease of metering and handling. Of course, when the chemical treatment agent is liquid at ordinary temperature, the chemical treatment agent can also be used in the form of a solution as occasion demands, and there is no particular limitation.

[0163] 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 magnesium compound or the magnesium-aluminum carrier.

[0164] Specific examples include C 5-12 paraffins, C 5-12 cycloparaffins, halogenated C 5-12 paraffins and halogenated C 5-12 cycloparaffins, and the like, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloro-undecane, chlorododecane, and chlorocyclohexane, and the like, with pentane, hexane, decane, and cyclohexane being preferred, and hexane being most preferred.

[0165] These solvents can be used singly or in combination in any ratio.

[0166] In addition, the concentration of the chemical treatment agent in the solution thereof is not particularly limited and can be appropriately selected as needed, as long as it enables the chemical treatment reaction to be performed in 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 can be directly used for the treatment, but it can also be used after being adjusted into a solution of the chemical treatment agent.

[0167] In general, the molar concentration of the chemical treatment agent in the solution thereof is generally set to 0.01 to 1.0 mol / L, but is not limited thereto.

[0168] As the method of performing the chemical treatment, for example, in the case of using a solid chemical treatment agent (e.g., 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, added dropwise) to the magnesium-aluminum carrier to be treated; in the case of using a liquid chemical treatment agent (e.g., titanium tetrachloride), a predetermined amount of the chemical treatment agent can be directly added (preferably, added dropwise) to the magnesium-aluminum carrier to be treated (but can also be added after being prepared into a solution).

[0169] In one embodiment of the present application, the treatment reaction is allowed to proceed (with stirring, if necessary) at a reaction temperature of -40 to 10°C (preferably, -20 to 0°C) for 0.5 to 24 hours, preferably 1 to 8 hours, and more preferably 2 to 6 hours, and then filtration, optional washing, and optional drying are performed as needed.

[0170] According to the present invention, the filtration, washing, and drying can be performed using conventional methods, wherein the washing solvent can be the same as or different from the solvent used to dissolve the chemical treatment agent. The washing is generally performed 1 to 8 times, preferably 2 to 6 times, and most preferably 2 to 4 times. The drying can be performed, for example, by drying the magnesium-supported non-metallocene catalyst to be treated under a vacuum of 2 to 100 mBar absolute pressure, preferably 5 to 50 mBar absolute pressure, for 2 to 30 hours, preferably 4 to 12 hours, to obtain a dried magnesium-supported non-metallocene catalyst.

[0171] According to the present invention, the amount of the chemical treatment agent used is such that the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as Group IVB metal (such as Ti) element is 1:1-20, preferably 1:2-10.

[0172] As known to those skilled in the art, all of the aforementioned method steps are preferably carried out under substantially anhydrous and oxygen-free conditions. Substantially anhydrous and oxygen-free herein means that the water and oxygen contents in the system are consistently less than 10 ppm. Furthermore, after preparation, the supported non-metallocene catalyst of the present invention typically needs to be stored under sealed conditions and a slightly positive pressure until ready for use.

[0173] In one embodiment, the present invention also relates to a magnesium-supported non-metallocene catalyst (sometimes also referred to as a supported non-metallocene olefin polymerization catalyst) produced by the aforementioned method for preparing a magnesium-supported non-metallocene catalyst.

[0174] In a further embodiment, the present invention relates to a method for homopolymerization / copolymerization of olefins, wherein the supported non-metallocene catalyst of the present invention is used as a catalyst for olefin polymerization to homopolymerize or copolymerize olefins.

[0175] With respect to the olefin homopolymerization / copolymerization method involved in the present invention, except for the contents specifically mentioned below, other unspecified contents (such as the polymerization reactor, olefin dosage, catalyst and olefin addition method, etc.) can be directly applied to those conventionally known in the art without any special limitations, and their description is omitted here.

[0176] In one embodiment, according to the homopolymerization / copolymerization method of the present invention, the magnesium carrier-supported non-metallocene catalyst of the present invention is used as a main catalyst, and one or more selected from aluminoxane, alkyl aluminum, halogenated alkyl aluminum, borofluorocarbon, alkyl boron and alkyl boron ammonium salt are used as cocatalysts to homopolymerize or copolymerize olefins.

[0177] The addition of the procatalyst and the cocatalyst to the polymerization reaction system can be by first adding the procatalyst and then adding the cocatalyst, or by first adding the cocatalyst and then adding the procatalyst, or by mixing both and then adding them together, or by adding them simultaneously. When the procatalyst and the cocatalyst are added separately, they can be added sequentially in the same addition line, or they can be added sequentially in multiple addition lines, and when they are added simultaneously, multiple addition lines should be selected. For continuous polymerization, multiple addition lines are preferred, and for batch polymerization, mixing both and then adding them together in the same addition line, or adding the cocatalyst first and then adding the procatalyst in the same addition line are preferred.

[0178] According to the present application, the reaction mode of the olefin homo / copolymerization method is not particularly limited, and those known in the art can be used, such as slurry method, emulsion method, solution method, bulk method, and gas phase method, among which the slurry method and the gas phase method are preferred.

[0179] According to the present application, as the olefin, C2to C 10 Monolefins, diolefins, cyclic olefins, and other olefinically unsaturated compounds.

[0180] Specifically, as the C2to C 10 Monolefins, such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and styrene; as the cyclic olefins, such as 1-cyclopentene and norbornene; as the diolefins, such as 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene, norbornadiene, and 1,7-octadiene; and as the other olefinically unsaturated compounds, such as vinyl acetate and (meth)acrylate. Among these, the homo-polymerization of ethylene, or the copolymerization of ethylene with propylene, 1-butene, or 1-hexene is preferred.

[0181] According to the present application, homo-polymerization refers to the polymerization of only one of the olefins, and copolymerization refers to the polymerization between two or more of the olefins.

[0182] According to the present application, the cocatalyst is selected from aluminoxane, alkylaluminum, halogenated alkylaluminum, boron fluoride alkane, alkylboron, and alkylboron ammonium salt, among which aluminoxane and alkylaluminum are preferred.

[0183] As the aluminoxane, linear aluminoxane represented by the following general formula (III-1) can be mentioned: (R)(R)Al-(Al(R)-O) n -O-Al(R)(R), and cyclic aluminoxane represented by the following general formula (III-2): -(Al(R)-O-)n+2 -.

[0184]

[0185] In the aforementioned general formula, the groups R are the same as or different from each other (preferably the same), and each is independently selected from the group consisting of C1-C8 alkyl, preferably methyl, ethyl and isobutyl, and most preferably methyl; and n is an arbitrary integer in the range of 1 to 50, preferably an arbitrary integer in the range of 10 to 30.

[0186] As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferred, methylaluminoxane and isobutylaluminoxane are further preferred, and methylaluminoxane is most preferred.

[0187] These aluminoxanes can be used singly or in combination of a plurality of kinds in any ratio.

[0188] As the alkylaluminum, the same compounds as those represented by the general formula (I) of the aforementioned alkylaluminum can be cited, such as trimethylaluminum (Al(CH3)3), triethylaluminum (Al(CH3CH2)3), tripropylaluminum (Al(C3H7)3), triisobutylaluminum (Al(i-C4H9)3), tri-n-butylaluminum (Al(C4H9)3), triisopentylaluminum (Al(i-C5H 11 )3), tri-n-pentylaluminum (Al(C5H 11 )3), trihexylaluminum (Al(C6H 13 )3), triisohexylaluminum (Al(i-C6H 13 )3), diethylmethylaluminum (Al(CH3)(CH3CH2)2) and dimethylethylaluminum (Al(CH3CH2)(CH3)2), etc., of which trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferred, triethylaluminum and triisobutylaluminum are further preferred, and triethylaluminum is most preferred.

[0189] These alkylaluminums can be used singly or in combination of a plurality of kinds in any ratio.

[0190] As the halogenated alkylaluminum, the boron fluoride alkyl, the alkyl boron and the alkyl boron ammonium salt, those conventionally used in the art can be used as they are without particular limitation.

[0191] In addition, according to the present application, the cocatalyst can be used singly or a plurality of the aforementioned cocatalysts can be used in combination as needed in any ratio without particular limitation.

[0192] According to the present application, depending on the reaction mode of the olefin homopolymerization / copolymerization method, sometimes a polymerization solvent needs to be used.

[0193] As the solvent for polymerization, those conventionally used in the art when carrying out the homopolymerization / copolymerization of olefins can be used without particular limitation.

[0194] As the solvent for polymerization, for example, C 4-10 alkanes (such as butane, pentane, hexane, heptane, octane, nonane or decane, etc.), halogenated C 1-10 alkanes (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), etc. Among them, hexane is preferably used as the solvent for polymerization.

[0195] These solvents for polymerization can be used singly or in combination in any proportion.

[0196] According to the present application, the polymerization reaction pressure in the process for the homopolymerization / copolymerization of olefins is generally 0.1-10 MPa, preferably 0.1-4 MPa, more preferably 1-3 MPa, but is not always limited thereto. According to the present application, the polymerization reaction temperature is generally -40°C-200°C, preferably 10°C-100°C, more preferably 40°C-90°C, but is not always limited thereto.

[0197] In addition, according to the present application, the process for the homopolymerization / copolymerization of olefins can be carried out in the presence of hydrogen or in the absence of hydrogen. In the presence of hydrogen, the partial pressure of hydrogen can be 0.01%-99% of the polymerization reaction pressure, preferably 0.01%-50%, but is not always limited thereto.

[0198] According to the present application, in carrying out the process for the homopolymerization / copolymerization of olefins, the molar ratio of the cocatalyst calculated as aluminum or boron to the supported non-metallocene catalyst calculated as Group IVB metal is generally 1:1-1000, preferably 1:1-500, more preferably 1:10-500, but is not always limited thereto.

[0199] Examples

[0200] The present application is further illustrated in detail by the following examples, but the present application is not limited to these examples.

[0201] The polymer bulk density (unit: g / cm 3 ) was measured in accordance with the Chinese National Standard GB1636-79.

[0202] The contents of Group IVB metal (such as Ti) and Mg elements in the magnesium carrier supported non-metallocene catalyst were measured by ICP-AES method, and the content of non-metallocene ligand was measured by elemental analysis method.

[0203] The polymerization activity of the catalyst was calculated as follows: after the polymerization reaction was completed, the polymerization product in the reaction kettle was filtered and dried, then the mass of the polymerization product was weighed, and the polymerization activity of the catalyst was represented by the ratio of the mass of the polymerization product to the mass of the used supported non-metallocene catalyst (unit: kg polymer / g catalyst or kg polymer / g Cat).

[0204] The viscosity average molecular weight of the polymer was calculated as follows: the intrinsic viscosity of the polymer was determined according to the standard ASTM D4020-00 by using a high-temperature dilution type Ubbelohde viscometer method (capillary inner diameter: 0.44 mm, constant temperature bath medium: 300# silicone oil, dilution solvent: decalin, determination temperature: 135°C), and then the viscosity average molecular weight Mv of the polymer was calculated according to the following formula.

[0205] Mv = 5.37 x 10 4 [η] 1.37

[0206] wherein η is the intrinsic viscosity.

[0207] The determination of the alcohol content in the carrier was carried out as follows: quantitative analysis was carried out by using capillary gas chromatography, the instrument was an Agilent 6890N gas chromatograph equipped with an automatic sampler and a hydrogen flame ionization detector (FID); the chromatographic column was DB-1 (30 m x 0.32 mm x 0.25 μm), and the gas chromatography operating conditions were as follows: temperature: vaporization chamber 250°C, column temperature 60°C, detector 250°C; carrier gas: high-purity nitrogen; carrier gas flow rate: 1.4 ml / min; split ratio: 70:1; sample injection amount: 0.2 ml; test reagent: chromatographically pure ethanol or n-butanol, wherein ethanol was used to determine the ethanol content, n-butanol was used to determine the n-butanol content, and ethanol or n-butanol could be used to determine the content of other alcohols. The relative retention time was determined as 2.426 min for ethanol and 3.151 min for n-butanol. Ten different concentrations of the alcohol to be tested were accurately prepared in the reagent alcohol solution as standards, and under the gas chromatography conditions, the correction factors of each component were calculated by using the area normalization method, and a graph of alcohol concentration index versus actual concentration was drawn. 1.00 g of the carrier was accurately weighed, 10 ml of the alcohol reagent was added, and after stirring and dissolving at room temperature for 20 min, the solution was filtered, and the filtrate was used. Under the gas chromatography conditions, the quantitative filtrate was added to the automatic sampler for automatic program sampling, and the alcohol concentration index of the filtrate was calculated by dividing the peak area of the alcohol to be tested by the total area, and the actual alcohol concentration was obtained by substituting into the graph, and finally the alcohol content in the carrier was obtained after conversion.

[0208] The polymer particle size distribution and fine powder content were measured on a Microtrac S3500 laser particle size analyzer, the particle size measurement range was 0.01-10000 microns, and the volume ratio of the polymer with a particle size less than 75 microns to the total polymer volume was taken as the fine powder content.

[0209] Example 1

[0210] The magnesium compound and non-metallocene ligand were weighed at 4.76 g, alcohol was added, and after being dissolved under stirring at 60°C, a dilution solvent was added, and after being stirred uniformly, it was warmed to 80°C, and dried under vacuum at an absolute pressure of 10 mBar for 2 h, to obtain a magnesium carrier, wherein the alcohol content was 1.57 wt%.

[0211] 50 ml of hexane solvent was measured and added to the magnesium carrier, and then alkyl aluminum was added dropwise under stirring and at room temperature for 15 min, and then warmed to room temperature for 0.5 h, warmed to 40°C for 0.5 h, warmed to 60°C for 0.5 h, and finally warmed to 80°C for 1 h, wherein the warming rate was 20°C / h. After stopping stirring and heating, the obtained mixed product was filtered and washed with hexane 3 times, each time using 100 ml of hexane, to obtain a magnesium aluminum carrier.

[0212] 50 ml of hexane solvent was measured and added to the magnesium carrier, and then alkyl aluminum was added dropwise under stirring and at room temperature for 15 min, and then warmed to room temperature for 0.5 h, warmed to 40°C for 0.5 h, warmed to 60°C for 0.5 h, and finally warmed to 80°C for 1 h, wherein the warming rate was 20°C / h. After stopping stirring and heating, the obtained mixed product was filtered and washed with hexane 3 times, each time using 100 ml of hexane, to obtain a magnesium aluminum carrier.

[0213] The magnesium compound used was anhydrous magnesium chloride (MgCl2), the non-metallocene ligand used was a compound with the structural formula , the alcohol used was anhydrous ethanol, the dilution solvent used was decane, the alkyl aluminum used was triethyl aluminum, and the chemical treatment agent used was titanium tetrachloride (TiCl4).

[0214] The molar ratio of the magnesium compound to the alcohol, calculated based on the Mg element, was 1:17.1; the molar ratio of the magnesium compound to the non-metallocene ligand, calculated based on the Mg element, was 1:0.05; the ratio of the magnesium compound to the dilution solvent was 1 mol:2 L; the molar ratio of the magnesium compound to the triethyl aluminum, calculated based on the Mg element and the Al element, was 1:2; and the molar ratio of the magnesium compound to the chemical treatment agent titanium tetrachloride, calculated based on the Mg element and the Ti element, was 1:7.2.

[0215] This catalyst is denoted as CAT-1.

[0216] Example 2

[0217] The same as Example 1, but with the following changes:

[0218] wherein the non-metallocene ligand is a compound having the structural formula The magnesium compound is n-butyl magnesium, the alcohol is anhydrous butanol, the dilution solvent is heptane, and the alkyl aluminum is triisobutyl aluminum. The alcohol content in the magnesium carrier is 1.39 wt%.

[0219] The molar ratio of the magnesium compound to the alcohol is 1:28.4 in terms of Mg element; the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.075 in terms of Mg element; the ratio of the magnesium compound to the dilution solvent is 1 mol:3 L; the molar ratio of the magnesium compound to the alkyl aluminum in terms of Mg element to Al element is 1:3; and the molar ratio of the magnesium compound to the chemical treatment agent titanium tetrachloride in terms of Mg element to Ti element is 1:4.

[0220] This catalyst is denoted as CAT-2.

[0221] Example 3

[0222] The same as Example 1, but with the following changes:

[0223] The magnesium compound is anhydrous ethoxymagnesium (Mg(OC2H5)2), the non-metallocene ligand is a compound having the structural formula The alcohol is anhydrous propanol, the dilution solvent is cyclohexane, and the alkyl aluminum is tri-n-hexyl aluminum (Al(C6H 13 )3). The chemical treatment agent is zirconium tetrachloride (ZrCl4). The alcohol content in the magnesium carrier is 1.21 wt%.

[0224] The molar ratio of the magnesium compound to the alcohol is 1:22.6 in terms of Mg element; the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.12 in terms of Mg element; the ratio of the magnesium compound to the dilution solvent is 1 mol:1 L; the molar ratio of the magnesium compound to the alkyl aluminum in terms of Mg element to Al element is 1:1; and the molar ratio of the magnesium compound to the chemical treatment agent zirconium tetrachloride in terms of Mg element to Zr element is 1:9.5.

[0225] This catalyst is denoted as CAT-3.

[0226] Example 4

[0227] The same as Example 1, but with the following changes:

[0228] The dilution solvent is changed to toluene.

[0229] The molar ratio of the magnesium compound to the alcohol is 1 : 10.26 in terms of Mg element, the ratio of the magnesium compound to the dilution solvent is 1 mol: 2.5 L, the molar ratio of the magnesium compound to the chemical treating agent titanium tetrachloride in terms of Ti element is 1:4, the molar ratio of the magnesium compound to the non-metallocene ligand in terms of Mg element is 1:0.075, and the alcohol content in the magnesium carrier is 1.14 wt%.

[0230] The catalyst is recorded as CAT-5.

[0231] Example 5

[0232] The example is basically the same as Example 2, but has the following changes:

[0233] The dilution solvent is changed to ethylbenzene, and the non-metallocene ligand is a compound with the structural formula of .

[0234] The molar ratio of the magnesium compound to the alcohol is 1 : 10.26 in terms of Mg element, the ratio of the magnesium compound to the dilution solvent is 1 mol: 2.5 L, the molar ratio of the magnesium compound to the chemical treating agent titanium tetrachloride in terms of Ti element is 1:4, the molar ratio of the magnesium compound to the non-metallocene ligand in terms of Mg element is 1:0.075, and the alcohol content in the magnesium carrier is 1.14 wt%.

[0235] The catalyst is recorded as CAT-5.

[0236] Example 6

[0237] The example is basically the same as Example 3, but has the following changes:

[0238] The dilution solvent is changed to ethylbenzene, and the non-metallocene ligand is a compound with the structural formula of .

[0239] The molar ratio of the magnesium compound to the alcohol is 1 : 10.26 in terms of Mg element, the ratio of the magnesium compound to the dilution solvent is 1 mol: 2.5 L, the molar ratio of the magnesium compound to the chemical treating agent titanium tetrachloride in terms of Ti element is 1:4, the molar ratio of the magnesium compound to the non-metallocene ligand in terms of Mg element is 1:0.075, and the alcohol content in the magnesium carrier is 1.14 wt%.

[0240] The catalyst is recorded as CAT-5.

[0241] Comparative Example 1-1

[0242] The example is basically the same as Example 1, but has the following changes:

[0243] The magnesium support was instead dried under vacuum at 5 mBar absolute for 10 h, obtaining a magnesium support having an alcohol content of 0.74 wt%.

[0244] The catalyst is denoted as CAT-1-A.

[0245] Comparative Example 1-2

[0246] The procedure of Example 1 was substantially repeated, with the following changes:

[0247] The magnesium support was instead dried under vacuum at 10 mBar absolute for 1 h, obtaining a magnesium support having an alcohol content of 4.2 wt%.

[0248] The catalyst is denoted as CAT-1-B.

[0249] Comparative Example 1-3

[0250] The procedure of Example 1 was substantially repeated, with the following changes:

[0251] After the dropwise addition of the chemical treatment agent to the magnesium-aluminum support and hexane mixture at 25 °C, the reaction was carried out at 25 °C for 4 h.

[0252] The catalyst is denoted as CAT-1-C.

[0253] Example 7 (application example)

[0254] The supported non-metallocene catalysts CAT-1 to 6, CAT-1-A to C, and the cocatalyst were weighed out separately and used to carry out the homopolymerization of ethylene, the copolymerization of ethylene and the preparation of ultra-high molecular weight polyethylene according to the following methods under the following conditions.

[0255] The homopolymerization was carried out in a 5 L polymerization autoclave, slurry polymerization process, 2.5 L of hexane solvent, total polymerization pressure 0.8 MPa, polymerization temperature 85 °C, hydrogen partial pressure 0.2 MPa, reaction time 2 h. 2.5 L of hexane was first added to the polymerization autoclave, stirring was started, then 20 mg of the supported non-metallocene catalyst and the cocatalyst mixture were added, hydrogen was then added to 0.2 MPa, and finally ethylene was continuously fed to maintain the total polymerization pressure at 0.8 MPa. After the reaction was completed, the gas in the autoclave was vented, the polymer in the autoclave was discharged, and the mass was weighed after drying. The specific conditions of the polymerization reaction and the polymerization evaluation results are shown in Table 1.

[0256] Co-polymerization: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85℃, hydrogen partial pressure 0.2MPa, reaction time 2h. First, 2.5L hexane was added to the polymerization autoclave, and then the stirring was started. Then, 20mg supported non-metallocene catalyst and cocatalyst mixture were added. 50g of hexene-1 comonomer was added at one time. Hydrogen was added to 0.2MPa. Finally, ethylene was continuously introduced to keep the total polymerization pressure at 0.8MPa. After the reaction was completed, the gas in the autoclave was vented, and the polymer in the autoclave was discharged. After drying, the mass was weighed. The specific conditions of the polymerization reaction and the polymerization evaluation results are shown in Table 1.

[0257] Preparation of ultra-high molecular weight polyethylene polymerization: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.5MPa, polymerization temperature 70℃, reaction time 6h. First, 2.5L hexane was added to the polymerization autoclave, and then the stirring was started. Then, 20mg supported non-metallocene catalyst and cocatalyst mixture were added. The molar ratio of cocatalyst to active metal of the catalyst was 100. Finally, ethylene was continuously introduced to keep the total polymerization pressure at 0.5MPa. After the reaction was completed, the gas in the autoclave was vented, and the polymer in the autoclave was discharged. After drying, the mass was weighed. The specific conditions of the polymerization reaction and the polymerization evaluation results are shown in Table 2.

[0258] Table 1. Effectiveness of magnesium carrier supported non-metallocene catalyst for olefin polymerization

[0259]

[0260] Table 2. Effectiveness of magnesium carrier supported non-metallocene catalyst for preparation of ultra-high molecular weight polyethylene polymerization

[0261]

[0262] From the comparison of the effects obtained in Table 1, Nos. 1 and 3, it can be seen that the copolymerization effect of the catalyst is significant, that is, the copolymerization activity of the catalyst is higher than the homopolymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, that is, improve the particle morphology of the polymer.

[0263] From the comparison of the effects obtained in Table 1, Nos. 1 and 2, it can be seen that the polymerization performance obtained under the conditions of molar ratio of cocatalyst to active metal of the catalyst of 40 and 100 is comparable, which shows that the amount of cocatalyst required when the catalyst provided by the present application is used for olefin polymerization is less.

[0264] From the comparison of the effects obtained in Table 1, Nos. 1 and 3, it can be seen that the copolymerization effect of the catalyst is significant, that is, the copolymerization activity of the catalyst is higher than the homopolymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, that is, improve the particle morphology of the polymer. Figure 1 and Figure 2 It can be seen that the polymer obtained by using the magnesium carrier supported non-metallocene catalyst provided by the present application has a fine average particle size and uniform distribution.

[0265] As can be seen from Table 1, No. 1 and No. 11, 12, and Table 2, No. 1 and No. 7, 8, too low or too high alcohol content in the magnesium carrier can result in a decrease in polymerization activity and polymer bulk density, and an increase in fine powder content; in the preparation of ultra-high molecular weight polyethylene, polymerization activity, polymer bulk density, and polymer viscosity average molecular weight are all decreased.

[0266] Although the specific embodiments of the present application have been described in detail above with reference to the embodiments, it should be pointed out that the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims attached herewith. Those skilled in the art can make appropriate changes to these embodiments without departing from the technical thought and the main idea of the present application, and these changed embodiments are obviously included in the protection scope of the present application.

Claims

1. A method for preparing a magnesium carrier-supported non-metallocene catalyst, comprising the following steps: The step of dissolving the magnesium compound and the non-metallocene ligand in alcohol, adding a diluent solvent, mixing, and then drying to obtain a magnesium support, wherein the weight ratio of the alcohol content in the magnesium support relative to the magnesium support is 1.1-2.5 wt %; The step of adding alkyl aluminum to a magnesium support to react, and filtering to obtain a magnesium aluminum support; The step of treating the magnesium-aluminum support with a chemical treatment agent selected from Group IVB metal compounds at -40 to 10° C. to obtain the magnesium support-supported non-metallocene catalyst, The non-metallocene ligand is selected from one or more compounds having the following chemical formula: The chemical treatment agent for the Group IVB metal compound is selected from one or more of Group IVB metal halides, Group IVB metal alkyl compounds, Group IVB metal alkoxy compounds, Group IVB metal alkyl halides and Group IVB metal alkoxy halides.

2. The preparation method according to claim 1, characterized in that: The magnesium compound is selected from one or more of magnesium halide, alkoxymagnesium halide, alkoxymagnesium, alkylmagnesium, alkylmagnesium halide and alkylalkoxymagnesium.

3. The preparation method according to claim 1 or 2, characterized in that: The alcohol is selected from one or more of aliphatic alcohols, aromatic alcohols and alicyclic alcohols, wherein the alcohol is optionally selected from halogen atoms or C 1-6 The substituents of the alkoxy group are substituted.

4. The preparation method according to claim 1 or 2, wherein the dilution solvent is selected from one or more of paraffins, cycloalkanes, halogenated paraffins, halogenated cycloalkanes, and aromatic hydrocarbons.

5. The preparation method according to claim 1, characterized in that: The content of alcohol in the magnesium carrier is 1.5-2.0 wt% relative to the weight of the magnesium carrier; and / or The step of treating the magnesium-aluminum support with a chemical treatment agent selected from Group IVB metal compounds at -20 to 0°C to obtain the magnesium support-supported non-metallocene catalyst; and / or The magnesium compound is one or more selected from magnesium chloride, ethoxymagnesium and n-butylmagnesium; and / or The alcohol is selected from one or more of ethanol, propanol and butanol; and / or The dilution solvent is selected from one or more of hexane, heptane, decane, cyclohexane, toluene, ethylbenzene, and xylene.

6. The preparation method according to claim 1 or 2, characterized in that: The alkylaluminum is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisohexylaluminum, diethylmethylaluminum and dimethylethylaluminum.

7. The preparation method according to claim 1 or 2, characterized in that: The molar ratio of the magnesium compound calculated as Mg element to the non-metallocene ligand is 1:0.01-0.20, the molar ratio of the magnesium compound calculated as Mg element to the alcohol is 1:10-50, and the ratio of the magnesium compound to the dilution solvent is 1 mol: 0.5 to 4 L, the molar ratio of the magnesium compound calculated as Mg element to the alkyl aluminum calculated as aluminum element is 1:0.5 to 5; the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as Group IVB metal element is 1:1 to 20.

8. The preparation method according to claim 1 or 2, characterized in that: The alkylaluminum is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and tri-n-hexylaluminum; and / or The chemical treatment agent of the Group IVB metal compound is selected from one or more of TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4 and HfBr4; and / or The molar ratio of the magnesium compound calculated as Mg element to the non-metallocene ligand is 1:0.03-0.15, the molar ratio of the magnesium compound calculated as Mg element to the alcohol is 1:15-30, the ratio of the magnesium compound to the dilution solvent is 1 mol:1-3L, the molar ratio of the magnesium compound calculated as Mg element to the alkyl aluminum calculated as aluminum element is 1:1-3, and the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as Group IVB metal element is 1:2-10.

9. A magnesium carrier-supported non-metallocene catalyst produced by the preparation method according to any one of claims 1 to 8.

10. An olefin polymerization method, characterized in that: The method comprises the steps of homopolymerizing or copolymerizing olefins using the magnesium carrier-supported non-metallocene catalyst according to claim 9 as a main catalyst and one or more selected from aluminoxane, alkyl aluminum, halogenated alkyl aluminum, borofluorocarbon, alkyl boron and alkyl boron ammonium salt as a cocatalyst.

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