Magnesium single-carrier in-situ supported non-metallocene catalyst and preparation method and application thereof

[0030] The invention relates to a preparation method of a magnesium single carrier in-situ supported non-metallocene catalyst, comprising the following steps:

[0031] Dissolving the magnesium compound and the non-metallocene ligand in tetrahydrofuran to obtain a magnesium compound solution; drying the magnesium compound solution, or adding a precipitating agent to the magnesium compound solution and drying the resulting solid product to obtain a modified carrier step, wherein the tetrahydrofuran content in the modified carrier is 0.10-0.50wt%; and the modified carrier is treated with a chemical treatment agent selected from group IV B metal compounds to obtain the magnesium single carrier in situ loaded amphocene Metal catalyst steps.

[0032] According to the invention, no alcohol is used in said step of obtaining the magnesium compound solution.

[0033] The steps for obtaining the magnesium compound solution are specifically described below.

[0034] According to this procedure, a magnesium compound and a non-metallocene ligand are dissolved in tetrahydrofuran, thereby obtaining the magnesium compound solution.

[0035] When preparing the magnesium compound solution, the ratio of the magnesium compound (solid) to THF in terms of magnesium element is generally 1 mol:0.5-10L, preferably 1 mol:1-8L, more preferably 1 mol:2-6L.

[0036] According to the present invention, as the amount of the non-metallocene ligand used, the molar ratio of the magnesium compound (solid) in terms of Mg element to the non-metallocene ligand reaches 1:0.0001-1, preferably 1:0.0002 -0.4, more preferably 1:0.0008-0.2, still more preferably 1:0.001-0.1.

[0037] The preparation time of the magnesium compound solution (ie, the dissolution time of the magnesium compound and the non-metallocene ligand) is not particularly limited, but is generally 0.5-24 h, preferably 4-24 h. During the preparation process, stirring can be used to promote the dissolution of the magnesium compound and the non-metallocene ligand. The stirring can be in any form, such as a stirring paddle (rotational speed is generally 10-1000rpm) and the like. Dissolution can sometimes be facilitated by appropriate heating as needed.

[0038] The magnesium compound will be specifically described below.

[0039] According to the present invention, the term "magnesium compound" refers to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a carrier of a supported olefin polymerization catalyst using a common concept in the art.

[0040] According to the present invention, examples of the magnesium compound include magnesium halides, alkoxymagnesium halides, alkoxymagnesiums, alkylmagnesiums, alkylmagnesium halides and alkylalkoxymagnesiums.

[0041] Specifically, examples of the magnesium halide include magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), magnesium iodide (MgI 2 ) and magnesium fluoride (MgF 2 ), etc., wherein magnesium chloride is preferred.

[0042] As the alkoxymagnesium halide, for example, methoxymagnesium chloride (Mg(OCH 3 )Cl), ethoxymagnesium chloride (Mg(OC 2 h 5 )Cl), propoxymagnesium chloride (Mg(OC 3 h 7 )Cl), n-butoxymagnesium chloride (Mg(OC 4 h 9 )Cl), isobutoxymagnesium chloride (Mg(i-OC 4 h 9 )Cl), methoxymagnesium bromide (Mg(OCH 3 )Br), ethoxymagnesium bromide (Mg(OC 2 h 5 )Br), propoxymagnesium bromide (Mg(OC 3 h 7 )Br), n-butoxymagnesium bromide (Mg(OC 4 h 9 )Br), isobutoxymagnesium bromide (Mg(i-OC 4 h 9 )Br), methoxymagnesium iodide (Mg(OCH 3 ) I), ethoxymagnesium iodide (Mg(OC 2 h 5 ) I), propoxymagnesium iodide (Mg(OC 3 h 7 ) I), n-butoxymagnesium iodide (Mg(OC 4 h 9 )I) and isobutoxymagnesium iodide (Mg(i-OC 4 h 9 ) I), etc., among which methoxymagnesium chloride, ethoxymagnesium chloride and isobutoxymagnesium chloride are preferred.

[0043] As the magnesium alkoxide, for example, magnesium methoxide (Mg(OCH 3 ) 2 ), magnesium ethoxide (Mg(OC ) 2 h 5 ) 2 ), magnesium propoxide (Mg(OC 3 h 7 ) 2 ), magnesium butoxide (Mg(OC ) 4 h 9 ) 2 ), magnesium isobutoxide (Mg(i-OC 4 h 9 ) 2 ) and 2-ethylhexyloxymagnesium (Mg(OCH 2 CH(C 2 h 5 )C 4 h - ) 2 ), etc., among which ethoxymagnesium and isobutoxymagnesium are preferred.

[0044] As the alkylmagnesium, for example, methylmagnesium (Mg(CH 3 ) 2 ), ethylmagnesium (Mg(C 2 h 5 ) 2 ), propylmagnesium (Mg(C 3 h 7 ) 2 ), n-butylmagnesium (Mg(C 4 h 9 ) 2 ) and isobutylmagnesium (Mg(i-C 4 h 9 ) 2 ), etc., wherein ethylmagnesium and n-butylmagnesium are preferred.

[0045] As the alkylmagnesium halide, for example, methylmagnesium chloride (Mg(CH 3 )Cl), ethylmagnesium chloride (Mg(C 2 h 5 )Cl), propylmagnesium chloride (Mg(C 3 h 7 )Cl), n-butylmagnesium chloride (Mg(C 4 h 9 )Cl), isobutylmagnesium chloride (Mg(i-C 4 h 9 )Cl), methylmagnesium bromide (Mg(CH 3 )Br), ethylmagnesium bromide (Mg(C 2 h 5 ) Br), propylmagnesium bromide (Mg(C 3 h 7 ) Br), n-butylmagnesium bromide (Mg(C 4 h 9 )Br), isobutylmagnesium bromide (Mg(i-C 4 h 9 )Br), methylmagnesium iodide (Mg(CH 3 ) I), ethylmagnesium iodide (Mg(C 2 h 5 ) I), propylmagnesium iodide (Mg(C 3 h 7 ) I), n-butylmagnesium iodide (Mg(C 4 h 9 ) I) and isobutylmagnesium iodide (Mg(i-C 4 h 9 ) I), etc., wherein methylmagnesium chloride, ethylmagnesium chloride and isobutylmagnesium chloride are preferred.

[0046] As the alkyl alkoxymagnesium, for example, methylmethoxymagnesium (Mg(OCH 3 )(CH 3 )), Magnesium Methyl Ethoxide (Mg(OC 2 h 5 )(CH 3 )), Magnesium Methylpropoxide (Mg(OC 3 h 7 )(CH 3 )), methyl n-butoxymagnesium (Mg(OC 4 h 9 )(CH 3 )), methyl isobutoxymagnesium (Mg(i-OC 4 h 9 )(CH 3 )), magnesium ethyl methoxide (Mg(OCH 3 )(C 2 h 5 )), magnesium ethyl ethoxide (Mg(OC 2 h 5 )(C 2 h 5 )), Magnesium Ethylpropoxide (Mg(OC 3 h 7 )(C 2 h 5 )), ethyl n-butoxymagnesium (Mg(OC 4 h 9 )(C 2 h 5 )), ethyl isobutoxymagnesium (Mg(i-OC 4 h 9 )(C 2 h 5 )), magnesium propylmethoxide (Mg(OCH 3 )(C 3 h 7 )), Magnesium Propyl Ethoxide (Mg(OC 2 h 5 )(C 3 h 7 )), magnesium propylpropoxide (Mg(OC 3 h 7 )(C 3 h 7 )), propyl n-butoxymagnesium (Mg(OC 4 h 9 )(C 3 h 7 )), propylisobutoxymagnesium (Mg(i-OC 4 h 9 )(C 3 h 7 )), n-butylmagnesium methoxide (Mg(OCH 3 )(C 4 h 9 )), n-butyl magnesium ethoxide (Mg(OC 2 h 5 )(C 4 h 9 )), n-butylpropoxymagnesium (Mg(OC 3 h 7 )(C 4 h 9 )), n-butyl n-butoxymagnesium (Mg(OC 4 h 9 )(C 4 h 9 )), n-butylisobutoxymagnesium (Mg(i-OC 4 h 9 )(C 4 h 9 )), isobutylmagnesium methoxide (Mg(OCH 3 )(i-C 4 h 9 )), magnesium isobutylethoxide (Mg(OC 2 h 5 )(i-C 4 h 9)), isobutylpropoxymagnesium (Mg(OC 3 h 7 )(i-C 4 h 9 )), isobutyl n-butoxymagnesium (Mg(OC 4 h 9 )(i-C 4 h 9 )) and isobutylisobutoxymagnesium (Mg(i-OC 4 h 9 )(i-C 4 h 9 )) etc., among which butyl ethoxymagnesium is preferred.

[0047] These magnesium compounds may be used alone or in combination, and are not particularly limited.

[0048] When used in multiple mixed forms, the molar ratio between any two magnesium compounds in the magnesium compound mixture is 0.25-4:1, preferably 0.5-3:1, more preferably 1-2:1.

[0049] According to the present invention, the term "non-metallocene complex" refers to a single-center olefin polymerization catalyst relative to metallocene catalysts, which does not contain cyclopentadienyl groups such as cyclocene rings, fluorene rings, or indene rings, or derivatives thereof. metallocene compounds and are capable of exhibiting catalytic activity for olefin polymerization when combined with cocatalysts such as those described below (thus the non-metallocene complexes are sometimes also referred to as non-metallocene olefin polymerizable complexes ). The compound comprises a central metal atom and at least one multi-dentate ligand (preferably a tridentate ligand or a higher-dentate ligand) bonded to the central metal atom with a coordinate bond, and the term "non-metallocene ligand" is The aforementioned polydentate ligands.

[0050] According to the present invention, the non-metallocene ligand is selected from compounds having the following chemical structural formula:

[0051]

[0052] According to the present invention, the groups A, D and E (coordinating groups) in the compound are compatible with the present invention through the coordinating atoms (such as heteroatoms such as N, O, S, Se and P) contained in the compound. The IV B group metal atom contained in the IV B group metal compound used as a chemical treatment agent undergoes a coordination reaction to form a coordination bond, thus forming a complex with the IV B group metal atom as the central metal atom M (i.e. the present invention) Invention described non-metallocene complexes).

[0053] In a more specific embodiment, the non-metallocene ligand is selected from compounds (A) and compounds (B) having the following chemical structural formula:

[0054]

[0055] In a more specific embodiment, the non-metallocene ligand is selected from compounds (A-1) to compounds (A-4) and compounds (B-1) to compounds (B-4) having the following chemical structural formula ):

[0056]

[0057]

[0058]

[0059] In all the above chemical structures,

[0060] q is 0 or 1;

[0061] d is 0 or 1;

[0062] A is selected from oxygen atom, sulfur atom, selenium atom, -NR 23 R 24 , -N(O)R 25 R 26 , -PR 28 R 29 , -P(O)R 30 OR 31 , sulfone group, sulfoxide group or -Se(O)R 39 , wherein N, O, S, Se and P are each an atom for coordination;

[0063] B is selected from a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group or C 1 -C 30 hydrocarbon group;

[0064] D is selected from nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing group, C 1 -C 30 A hydrocarbon group, a sulfone group or a sulfoxide group, wherein N, O, S, Se and P are each a coordination atom;

[0065] E is selected from nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, phosphorus-containing groups or cyano groups (-CN), wherein N, O, S, Se and P are each used for coordination atom;

[0066] 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 coordination atom;

[0067] G from C 1 -C 30 Hydrocarbyl, substituted C 1 -C 30 Hydrocarbyl or inert functional groups;

[0068] Y is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each an atom for coordination;

[0069] Z is selected from nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, phosphorus-containing groups or cyano groups (-CN), such as -NR 23 R 24 , -N(O)R 25 R 26 、-PR 28 R 29 , -P(O)R 30 R 31 , -OR 34 、-SR 35 , -S(O)R 36 , -SeR 38 or -Se(O)R 39 , wherein N, O, S, Se and P are each an atom for coordination;

[0070] → represents a single or double bond;

[0071] - represents a covalent or ionic bond.

[0072] R 1 to R 4 , R 6 to R 21 each independently selected from hydrogen, C 1 -C 30 Hydrocarbyl, substituted C 1 -C 30 Hydrocarbyl (among which halogenated hydrocarbyl is preferred, such as -CH 2 Cl and -CH 2 CH 2 Cl) or an inert functional group. R 22 to R 36 , R 38 and R 39 each independently selected from hydrogen, C 1 -C 30 Hydrocarbyl or substituted C 1 -C 30 Hydrocarbyl (among which halogenated hydrocarbyl is preferred, such as -CH 2 Cl and -CH 2 CH 2 Cl). The above groups can be the same or different from each other, wherein adjacent groups such as R 1 with R 2 , R 6 with R 7 , R 7 with R 8 , R 8 with R 9 , R 13 with R 14 , R 14 with R 15 , R 15 with R 16 , R 18 with R 19 , R 19 with R 20 , R 20 with R 21 , R 23 with R 24 , or R 25 with R 26 etc. can be combined with each other to form a bond or a ring, preferably an aromatic ring, such as an unsubstituted benzene ring or 1-4 C 1 -C 30 Hydrocarbyl or substituted C 1 -C 30 Hydrocarbyl (among which halogenated hydrocarbyl is preferred, such as -CH 2 Cl and -CH 2 CH 2 Cl) substituted benzene ring.

[0073] R 5 selected from the lone pair of electrons on nitrogen, hydrogen, C 1 -C 30 Hydrocarbyl, substituted C 1 -C 30 A hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group. When R 5 When it is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R 5 N, O, S, P and Se in can be used as coordination atoms (coordinating with the central metal atom M).

[0074] In the context of the present invention, the inert functional groups can be selected from halogen, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, etc. Group, C 1 -C 10 Ester or nitro (-NO 2 ), etc., but usually excluding C 1 -C 30 Hydrocarbyl and Substituted C 1 -C 30 Hydrocarbyl.

[0075] In the context of the present invention, limited by the chemical structure of the multidentate ligand of the present invention, the inert functional group has the following characteristics:

[0076] (1) does not interfere with the coordination process of the group A, D, E, F, Y or Z with the central metal atom M, and

[0077] (2) The coordination ability with the central metal atom M is lower than that of the A, D, E, F, Y and Z groups, and does not replace the existing coordination of these groups with the central metal atom M .

[0078] According to the present invention, in all the aforementioned chemical structural formulas, according to specific circumstances, any adjacent two or more groups, such as R 21 with the group Z, or R 13 With the group Y, can be combined with each other to form a ring, preferably to form a C containing a heteroatom from the group Z or Y 6 -C 30 Aromatic heterocycles, such as pyridine rings, etc., wherein the aromatic heterocycles are optionally selected from one or more of C 1 -C 30 Hydrocarbyl and Substituted C 1 -C 30 Hydrocarbyl substituents are substituted.

[0079] In the context of the present invention,

[0080] 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-OR 34. The sulfur-containing group is selected from -SR 35 、-T-SR 35 , -S(O)R 36 or-T-SO 2 R 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 C 1 -C 30 Hydrocarbyl or substituted C 1 -C 30 Hydrocarbyl. The R 37 selected from hydrogen, C 1 -C 30 Hydrocarbyl or substituted C 1 -C 30 Hydrocarbyl.

[0081] In the context of the present invention, the C 1 -C 30 Hydrocarbyl is selected from C 1 -C 30 Alkyl (preferably C 1 -C 6 Alkyl, such as isobutyl), C 7 -C 30 Alkaryl (such as tolyl, xylyl, diisobutylphenyl, etc.), C 7 -C 30 Aralkyl (such as benzyl), C 3 -C 30 Cyclic alkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl (such as phenyl, naphthyl, anthracenyl, etc.), C 8 -C 30 Fused ring or C 4 -C 30 Heterocyclic group, wherein the heterocyclic group contains 1-3 heteroatoms selected from nitrogen atom, oxygen atom or sulfur atom, such as pyridyl, pyrrolyl, furyl or thienyl, etc.

[0082] According to the present invention, in the context of the present invention, according to the specific situation of the relevant group to which it is bound, said C 1 -C 30 Hydrocarbyl is sometimes referred to as C 1 -C 30 Hydrocarbon diradical (divalent group, or called C 1 -C 30 alkylene) or C 1 -C 30 Hydrocarbon triradicals (trivalent groups), as will be apparent to those skilled in the art.

[0083] In the context of the present invention, said substituted C 1 -C 30 Hydrocarbyl refers to C with one or more inert substituents 1 -C 30 Hydrocarbyl. The so-called inert substituents refer to these substituents for the aforementioned coordination groups (referring to the aforementioned groups A, D, E, F, Y and Z, or optionally also including R 5 ) has no substantial interference with the coordination process of the central metal atom M (i.e. the aforementioned IV B group metal atom); Affected by steric hindrance, etc.) undergoes a coordination reaction with the Group IV B metal atom to form a coordination bond. Generally, the inert substituent is selected from halogen or C 1 -C 30 Alkyl (preferably C 1 -C 6 alkyl, such as isobutyl).

[0084] In the context of the present invention, said silicon-containing groups are 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 the R 42 to R 54 each independently selected from hydrogen, the aforementioned C 1 -C 30 Hydrocarbyl or the aforementioned substituted C 1 -C 30 Hydrocarbyl, the above-mentioned groups may be the same or different from each other, and adjacent groups may combine with each other to form bonds or rings. Wherein the definition of the group T is the same as before.

[0085] As the non-metallocene ligand, for example, the following compounds can be mentioned:

[0086]

[0087]

[0088]

[0089]

[0090] The non-metallocene ligands are preferably selected from the following compounds:

[0091]

[0092]

[0093] The non-metallocene ligand is further preferably selected from the following compounds:

[0094]

[0095] The non-metallocene ligand is more preferably selected from the following compounds:

[0096]

[0097] One of these non-metallocene ligands may be used alone, or a plurality of them may be used in combination in an arbitrary ratio.

[0098] According to the present invention, the non-metallocene ligand is not a diether compound commonly used as an electron donor compound in the art.

[0099] The non-metallocene ligands can be produced by any method known to those skilled in the art. For the specific content of its manufacturing method, for example, refer to WO03/010207 and Chinese patents ZL01126323.7 and ZL02110844.7, etc., and the entirety of these documents is hereby incorporated by reference in this specification.

[0100] The magnesium compound solution is dried, or a precipitating agent is added to the magnesium compound solution to precipitate solid matter from the magnesium compound solution and the resulting solid product is dried to obtain a modified carrier.

[0101] The precipitating agent will be specifically described below.

[0102] According to the present invention, the term "precipitating agent" uses the general concept in the art, and refers to a chemical agent capable of reducing the solubility of a solute (such as the magnesium compound) in its solution and thereby causing it to precipitate out of the solution in solid form. Inert liquid.

[0103] According to the present invention, as the precipitating agent, for example, a solvent that is a poor solvent for the magnesium compound and a good solvent for tetrahydrofuran used to dissolve the magnesium compound, such as an alkane, Cycloalkanes, haloalkanes, and halocycloalkanes.

[0104] Examples of the alkane include pentane, hexane, heptane, octane, nonane, and decane, among which hexane, heptane, and decane are preferable, and hexane and decane are most preferable.

[0105] Examples of the cycloalkane include cyclohexane, cyclopentane, cycloheptane, cyclodecane, and cyclononane, among which cyclohexane is most preferred.

[0106] Examples of the halogenated alkanes include dichloromethane, dichlorohexane, dichloroheptane, chloroform, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, and dibromoheptane. , tribromomethane, tribromoethane and tribromobutane, etc.

[0107] As the halogenated cycloalkane, for example, chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, Cyclopentane, Bromocyclohexane, Bromocycloheptane, Bromocyclooctane, Bromocyclononane, Bromocyclodecane, etc.

[0108] These precipitating agents may be used alone, or may be mixed and used in an arbitrary ratio.

[0109] The way of adding the precipitating agent can be one-time addition or dropwise addition, preferably one-time addition. During the precipitation process, stirring can be used to promote the dispersion of the precipitating agent in the magnesium compound solution and facilitate the final precipitation of the solid product. The stirring can be in any form, such as a stirring paddle (rotational speed is generally 10-1000rpm) and the like.

[0110] The amount of the precipitating agent is not particularly limited, but generally by volume, the ratio of the precipitating agent to the tetrahydrofuran used to dissolve the magnesium compound is 1:0.2-5, preferably 1:0.5-2, more preferably 1:0.8~1.5.

[0111] The temperature of the precipitating agent is also not particularly limited, but normal temperature is generally preferred. Moreover, the precipitation process is also generally preferably carried out at normal temperature.

[0112] After complete precipitation, the obtained solid product is filtered, optionally washed, and dried to obtain a modified carrier. The filtering and washing methods are not particularly limited, and those conventionally used in the art can be used as needed.

[0113] The washing is generally performed 1 to 6 times, preferably 2 to 3 times, as required. Among them, the washing solvent is preferably the same solvent as the precipitating agent, but it may be different.

[0114] The drying method is not particularly limited, as long as the content of tetrahydrofuran in the modified carrier is reduced by drying the magnesium compound solution or by drying the solid product (optionally after washing). It is controlled to be 0.10-0.50wt%, preferably 0.10-0.40wt%, more preferably 0.11-0.35wt%.

[0115]According to the present invention, the drying can be carried out by conventional methods, such as inert gas drying method, vacuum drying method or heating drying method under vacuum, preferably inert gas drying method or heating drying method under vacuum, most preferably heating drying method under vacuum.

[0116] According to the present invention, the drying method (including drying temperature, drying vacuum and drying time) is limited as long as the tetrahydrofuran content of the modified carrier meets the aforementioned requirements of the present invention. For example, the magnesium compound solution is dried at a temperature of 15-60°C, preferably 35-55°C, at an absolute pressure of 2-100mBar, preferably at a vacuum of 5-50mBar, for 2-30h, preferably 4-12h, and then The modified carrier is obtained by drying at a temperature of 65-100° C., preferably 70-90° C., under vacuum at an absolute pressure of 2-100 mBar, preferably 5-50 mBar, for 1-20 hours, preferably 2-8 hours. Alternatively, a precipitating agent is added to the magnesium compound solution, and the obtained solid product (optionally after washing) is subjected to a temperature of 15-60° C., preferably 35-55° C., at an absolute pressure of 2-100 mBar, preferably 5 Under vacuum of -50mBar, dry for 2-30h, preferably 4-12h, then at a temperature of 65-100°C, preferably 70-90°C, at an absolute pressure of 2-100mBar, preferably under a vacuum of 5-50mBar, dry for 1- 20h, preferably 2-8h, thus obtaining the modified vector.

[0117] Next, the modified support is treated with a chemical treatment agent selected from group IV B metal compounds, thereby obtaining the magnesium single support in situ supported non-metallocene catalyst of the present invention.

[0118] According to the present invention, by chemically treating the modified support with the chemical treatment agent, the chemical treatment agent can react with the non-metallocene ligand contained in the modified support, thereby generating in situ on the support The non-metallocene complex (in-situ loading reaction), thus obtaining the magnesium single-support in-situ loading type non-metallocene catalyst of the present invention.

[0119] The chemical treatment agent will be specifically described below.

[0120] According to the present invention, group IV B metal compounds are used as the chemical treatment agent.

[0121] Examples of the Group IV B metal compound include Group IV B metal halides, Group IV B metal alkyl compounds, Group IV B metal alkoxy compounds, Group IV B metal alkyl halides, and Group IV B metal alkane compounds. Oxygen halides.

[0122] As the Group IV B metal halide, the Group IV B metal alkyl compound, the IV B Group metal alkoxy compound, the IV B Group metal alkyl halide and the IV B Group metal alkoxy Halides, for example, compounds of the following general formula (IV) structure can be enumerated:

[0123] M(OR 1 ) m x n R 2 4-m-n (IV)

[0124] in:

[0125] m is 0, 1, 2, 3 or 4;

[0126] n is 0, 1, 2, 3 or 4;

[0127] M is a group IV B metal in the periodic table of elements, such as titanium, zirconium and hafnium;

[0128] X is halogen, such as F, Cl, Br and I, etc.; and

[0129] R 1 and R 2 each independently selected from C 1-10 Alkyl, such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R 1 and R 2 Can be the same or different.

[0130] Specifically, examples of the Group IV B metal halides include titanium tetrafluoride (TiF 4 ), titanium tetrachloride (TiCl 4 ), titanium tetrabromide (TiBr 4 ), titanium tetraiodide (TiI 4 );

[0131] Zirconium tetrafluoride (ZrF 4 ), zirconium tetrachloride (ZrCl 4 ), zirconium tetrabromide (ZrBr 4 ), zirconium tetraiodide (ZrI 4 );

[0132] Hafnium tetrafluoride (HfF 4 ), hafnium tetrachloride (HfCl 4 ), hafnium tetrabromide (HfBr 4 ), hafnium tetraiodide (HfI 4 ).

[0133] As the group IV B metal alkyl compound, for example, tetramethyltitanium (Ti(CH 3 ) 4 ), tetraethyltitanium (Ti(CH 3 CH 2 ) 4 ), tetraisobutyltitanium (Ti(i-C 4 h 9 ) 4 ), tetra-n-butyltitanium (Ti(C 4 h 9 ) 4 ), triethylmethyltitanium (Ti(CH 3 )(CH 3 CH 2 ) 3 ), diethyldimethyltitanium (Ti(CH 3 ) 2 (CH 3 CH 2 ) 2 ), trimethylethyltitanium (Ti(CH 3 ) 3 (CH 3 CH 2 )), triisobutylmethyltitanium (Ti(CH 3 )(i-C 4 h 9 ) 3 ), diisobutyldimethyltitanium (Ti(CH 3 ) 2 (i-C 4 h 9 ) 2 ), trimethylisobutyltitanium (Ti(CH 3 ) 3 (i-C 4 h 9 )), triisobutylethyltitanium (Ti(CH 3 CH 2 )(i-C 4 h 9 ) 3 ), diisobutyldiethyltitanium (Ti(CH 3 CH 2 ) 2 (i-C 4 h 9 ) 2 ), triethylisobutyltitanium (Ti(CH 3 CH 2 ) 3 (i-C 4 h 9 )), tri-n-butylmethyltitanium (Ti(CH 3 )(C 4 h 9 ) 3 ), di-n-butyldimethyltitanium (Ti(CH 3 ) 2 (C 4 h 9 ) 2 ), trimethyl n-butyl titanium (Ti(CH 3 ) 3 (C 4 h 9 )), tri-n-butylmethyltitanium (Ti(CH 3 CH 2 )(C 4 h 9 ) 3 ), di-n-butyldiethyltitanium (Ti(CH 3 CH 2 ) 2 (C 4 h 9 ) 2 ), triethyl n-butyl titanium (Ti(CH 3 CH 2 ) 3 (C 4 h 9 ))Wait;

[0134] Tetramethylzirconium (Zr(CH 3 ) 4 ), Tetraethylzirconium (Zr(CH 3 CH 2 ) 4 ), Tetraisobutylzirconium (Zr(i-C 4 h 9 ) 4 ), tetra-n-butylzirconium (Zr(C 4 h 9 ) 4 ), triethylmethylzirconium (Zr(CH 3 )(CH 3 CH 2 ) 3 ), diethyldimethylzirconium (Zr(CH 3 ) 2 (CH 3 CH 2 ) 2 ), trimethylethylzirconium (Zr(CH 3 ) 3 (CH 3 CH 2 )), triisobutylmethylzirconium (Zr(CH 3 )(i-C 4 h 9 ) 3 ), diisobutyldimethylzirconium (Zr(CH 3 ) 2 (i-C 4 h 9 ) 2 ), Trimethylisobutylzirconium (Zr(CH 3 ) 3 (i-C 4 h 9 )), triisobutylethylzirconium (Zr(CH 3 CH 2 )(i-C 4 h 9 ) 3 ), diisobutyldiethylzirconium (Zr(CH 3 CH 2 ) 2 (i-C 4 h 9 ) 2 ), triethylisobutylzirconium (Zr(CH 3 CH 2 ) 3 (i-C 4 h 9 )), tri-n-butylmethylzirconium (Zr(CH 3 )(C 4 h 9 ) 3 ), di-n-butyldimethylzirconium (Zr(CH 3 ) 2 (C 4 h9 ) 2 ), trimethyl-n-butylzirconium (Zr(CH 3 ) 3 (C 4 h 9 )), tri-n-butylmethylzirconium (Zr(CH 3 CH 2 )(C 4 h 9 ) 3 ), di-n-butyldiethylzirconium (Zr(CH 3 CH 2 ) 2 (C 4 h 9 ) 2 ), triethyl n-butyl zirconium (Zr(CH 3 CH 2 ) 3 (C 4 h 9 ))Wait;

[0135] Tetramethylhafnium (Hf(CH 3 ) 4 ), tetraethyl hafnium (Hf(CH 3 CH 2 ) 4 ), tetraisobutyl hafnium (Hf(i-C 4 h 9 ) 4 ), tetra-n-butyl hafnium (Hf(C 4 h 9 ) 4 ), triethylmethylhafnium (Hf(CH 3 )(CH 3 CH 2 ) 3 ), diethyldimethylhafnium (Hf(CH 3 ) 2 (CH 3 CH 2 ) 2 ), trimethylethylhafnium (Hf(CH 3 ) 3 (CH 3 CH 2 )), triisobutylmethyl hafnium (Hf(CH 3 )(i-C 4 h 9 ) 3 ), diisobutyldimethylhafnium (Hf(CH 3 ) 2 (i-C 4 h 9 ) 2 ), Trimethylisobutyl hafnium (Hf(CH 3 ) 3 (i-C 4 h 9 )), triisobutylethyl hafnium (Hf(CH 3 CH 2 )(i-C 4 h 9 ) 3 ), diisobutyldiethylhafnium (Hf(CH 3 CH 2 ) 2 (i-C 4 h 9 ) 2 ), triethylisobutyl hafnium (Hf(CH 3 CH 2 ) 3 (i-C 4 h 9 )), tri-n-butylmethyl hafnium (Hf(CH 3 )(C 4 h 9 ) 3 ), di-n-butyldimethyl hafnium (Hf(CH 3 ) 2 (C 4 h 9 ) 2 ), trimethyl-n-butyl hafnium (Hf(CH 3 ) 3 (C 4 h 9 )), tri-n-butylmethyl hafnium (Hf(CH 3 CH 2 )(C 4 h 9 ) 3 ), di-n-butyldiethylhafnium (Hf(CH 3 CH 2 ) 2 (C 4 h 9 ) 2 ), triethyl n-butyl hafnium (Hf(CH 3 CH 2 ) 3 (C 4 h 9 ))Wait.

[0136] As the group IV B metal alkoxide compound, tetramethoxytitanium (Ti(OCH 3 ) 4 ), titanium tetraethoxide (Ti(OCH 3 CH 2 ) 4 ), titanium tetraisobutoxide (Ti(i-OC 4 h 9 ) 4 ), tetra-n-butoxytitanium (Ti(OC 4 h 9 ) 4 ), titanium triethoxymethoxide (Ti(OCH 3 )(OCH 3 CH 2 ) 3 ), diethoxydimethoxytitanium (Ti(OCH 3 ) 2 (OCH 3 CH 2 ) 2 ), trimethoxyethoxytitanium (Ti(OCH 3 ) 3 (OCH 3 CH 2 )), triisobutoxymethoxytitanium (Ti(OCH 3 ) (i-OC 4 h 9 ) 3 ), diisobutoxydimethoxytitanium (Ti(OCH 3 ) 2 (i-OC 4 h 9 ) 2 ), titanium trimethoxyisobutoxide (Ti(OCH 3 ) 3 (i-OC 4 h 9 )), triisobutoxyethoxytitanium (Ti(OCH 3 CH 2 ) (i-OC 4 h 9 ) 3 ), diisobutoxydiethoxytitanium (Ti(OCH 3 CH 2 ) 2 (i-OC 4 h 9 ) 2 ), titanium triethoxyisobutoxide (Ti(OCH 3 CH 2 ) 3 (i-OC 4 h 9 )), tri-n-butoxymethoxytitanium (Ti(OCH 3 )(OC 4 h 9 ) 3 ), di-n-butoxydimethoxytitanium (Ti(OCH 3 ) 2 (OC 4 h 9 ) 2 ), trimethoxy n-butoxytitanium (Ti(OCH 3 ) 3 (OC 4 h 9 )), tri-n-butoxymethoxytitanium (Ti(OCH 3 CH 2 )(OC 4 h 9 ) 3 ), di-n-butoxydiethoxytitanium (Ti(OCH 3 CH 2 ) 2 (OC 4 h 9 ) 2 ), triethoxy-n-butoxytitanium (Ti(OCH 3 CH 2 ) 3 (OC 4 h 9 ))Wait;

[0137] Tetramethoxyzirconium (Zr(OCH 3 ) 4 ), zirconium tetraethoxide (Zr(OCH 3 CH 2 ) 4 ), zirconium tetraisobutoxide (Zr(i-OC 4 h 9 ) 4 ), zirconium tetra-n-butoxide (Zr(OC 4 h 9 ) 4 ), zirconium triethoxymethoxide (Zr(OCH 3 )(OCH 3 CH 2 ) 3 ), diethoxydimethoxyzirconium (Zr(OCH 3 ) 2 (OCH 3 CH 2 ) 2 ), zirconium trimethoxyethoxy (Zr(OCH 3 ) 3 (OCH 3 CH 2 )), triisobutoxymethoxyzirconium (Zr(OCH 3 ) (i-OC 4 h 9 ) 3 ), diisobutoxydimethoxyzirconium (Zr(OCH 3 ) 2 (i-OC 4 h 9 ) 2 ), trimethoxyisobutoxyzirconium (Zr(OCH 3 ) 3 (i-C 4 h 9 )), triisobutoxyethoxyzirconium (Zr(OCH 3 CH 2 ) (i-OC 4 h 9 ) 3 ), diisobutoxydiethoxyzirconium (Zr(OCH 3 CH 2 ) 2 (i-OC 4 h 9 ) 2 ), zirconium triethoxyisobutoxide (Zr(OCH 3 CH 2 ) 3 (i-OC 4 h 9 )), tri-n-butoxymethoxyzirconium (Zr(OCH 3 )(OC 4 h9 ) 3 ), di-n-butoxydimethoxyzirconium (Zr(OCH 3 ) 2 (OC 4 h 9 ) 2 ), zirconium trimethoxy n-butoxide (Zr(OCH 3 ) 3 (OC 4 h 9 )), tri-n-butoxymethoxyzirconium (Zr(OCH 3 CH 2 )(OC 4 h 9 ) 3 ), di-n-butoxydiethoxyzirconium (Zr(OCH 3 CH 2 ) 2 (OC 4 h 9 ) 2 ), zirconium triethoxy n-butoxide (Zr(OCH 3 CH 2 ) 3 (OC 4 h 9 ))Wait;

[0138] Hafnium tetramethoxide (Hf(OCH 3 ) 4 ), hafnium tetraethoxide (Hf(OCH 3 CH 2 ) 4 ), hafnium tetraisobutoxide (Hf(i-OC 4 h 9 ) 4 ), hafnium tetra-n-butoxide (Hf(OC 4 h 9 ) 4 ), hafnium triethoxymethoxide (Hf(OCH 3 )(OCH 3 CH 2 ) 3 ), diethoxydimethoxyhafnium (Hf(OCH 3 ) 2 (OCH 3 CH 2 ) 2 ), trimethoxyethoxyhafnium (Hf(OCH 3 ) 3 (OCH 3 CH 2 )), triisobutoxymethoxyhafnium (Hf(OCH 3 ) (i-OC 4 h 9 ) 3 ), diisobutoxydimethoxyhafnium (Hf(OCH 3 ) 2 (i-OC 4 h 9 ) 2 ), hafnium trimethoxyisobutoxide (Hf(OCH 3 ) 3 (i-OC 4 h 9 )), triisobutoxyethoxyhafnium (Hf(OCH 3 CH 2 ) (i-OC 4 h 9 ) 3 ), diisobutoxydiethoxyhafnium (Hf(OCH 3 CH 2 ) 2 (i-OC 4 h 9 ) 2 ), hafnium triethoxyisobutoxide (Hf(OCH 3 CH 2 ) 3 (i-C 4 h 9 )), tri-n-butoxymethoxyhafnium (Hf(OCH 3 )(OC 4 h 9 ) 3 ), di-n-butoxydimethoxyhafnium (Hf(OCH 3 ) 2 (OC 4 h 9 ) 2 ), trimethoxy-n-butoxyhafnium (Hf(OCH 3 ) 3 (OC 4 h 9 )), tri-n-butoxymethoxyhafnium (Hf(OCH 3 CH 2 )(OC 4 h 9 ) 3 ), di-n-butoxydiethoxyhafnium (Hf(OCH 3 CH 2 ) 2 (OC 4 h 9 ) 2 ), triethoxy-n-butoxyhafnium (Hf(OCH 3 CH 2 ) 3 (OC 4 h 9 ))Wait.

[0139] As the group IV B metal alkyl halides, for example, trimethyltitanium chloride (TiCl(CH 3 ) 3 ), triethyltitanium chloride (TiCl(CH 3 CH 2 ) 3 ), triisobutyl titanium chloride (TiCl(i-C 4 h 9 ) 3 ), tri-n-butyl titanium chloride (TiCl(C 4 h 9 ) 3 ), dimethyl titanium dichloride (TiCl 2 (CH 3 ) 2 ), diethyltitanium dichloride (TiCl 2 (CH 3 CH 2 ) 2 ), diisobutyl titanium dichloride (TiCl 2 (i-C 4 h 9 ) 2 ), tri-n-butyl titanium chloride (TiCl(C 4 h 9 ) 3 ), methyl titanium trichloride (Ti(CH 3 ) Cl 3 ), ethyl titanium trichloride (Ti(CH 3 CH 2 ) Cl 3 ), isobutyl titanium trichloride (Ti(i-C 4 h 9 ) Cl 3 ), n-butyl titanium trichloride (Ti(C 4 h 9 ) Cl 3 );

[0140] Trimethyltitanium bromide (TiBr(CH 3 ) 3 ), triethyltitanium bromide (TiBr(CH 3 CH 2 ) 3 ), triisobutyltitanium bromide (TiBr(i-C 4 h 9 ) 3 ), tri-n-butyltitanium bromide (TiBr(C 4 h 9 ) 3 ), Dimethyl titanium dibromide (TiBr 2 (CH 3 ) 2 ), titanium diethylbromide (TiBr 2 (CH 3 CH 2 ) 2 ), diisobutyl titanium dibromide (TiBr 2 (i-C 4 h 9 ) 2 ), tri-n-butyltitanium bromide (TiBr(C 4 h 9 ) 3 ), methyl titanium tribromide (Ti(CH 3 )Br 3 ), ethyl titanium tribromide (Ti(CH 3 CH 2 )Br 3 ), isobutyl titanium tribromide (Ti(i-C 4 h 9 )Br 3 ), n-butyl titanium tribromide (Ti(C 4 h 9 )Br 3 );

[0141] Trimethylzirconium chloride (ZrCl(CH 3 ) 3 ), triethylzirconium chloride (ZrCl(CH 3 CH 2 ) 3 ), triisobutylzirconium chloride (ZrCl(i-C 4 h 9 ) 3 ), tri-n-butylzirconium chloride (ZrCl(C 4 h 9 ) 3 ), dimethyl zirconium dichloride (ZrCl 2 (CH 3 ) 2 ), diethyl zirconium dichloride (ZrCl 2 (CH 3 CH 2 ) 2 ), diisobutylzirconium dichloride (ZrCl 2 (i-C 4 h 9 ) 2 ), tri-n-butylzirconium chloride (ZrCl(C 4 h 9 ) 3 ), methyl zirconium trichloride (Zr(CH 3 ) Cl 3 ), ethyl zirconium trichloride (Zr(CH 3 CH 2 ) Cl 3 ), isobutylzirconium trichloride (Zr(i-C 4 h 9 ) Cl 3 ), n-butylzirconium trichloride (Zr(C 4 h 9 ) Cl 3 );

[0142] Trimethylzirconium bromide (ZrBr(CH 3 ) 3 ), triethylzirconium bromide (ZrBr(CH 3 CH 2 ) 3 ), triisobutylzirconium bromide (ZrBr(i-C 4 h 9 ) 3 ), tri-n-butylzirconium bromide (ZrBr(C 4 h 9 ) 3 ), Dimethyl zirconium dibromide (ZrBr 2 (CH 3 )2 ), diethyl zirconium dibromide (ZrBr 2 (CH 3 CH 2 ) 2 ), diisobutyl zirconium dibromide (ZrBr 2 (i-C 4 h 9 ) 2 ), tri-n-butylzirconium bromide (ZrBr(C 4 h 9 ) 3 ), methyl zirconium tribromide (Zr(CH 3 )Br 3 ), ethyl zirconium tribromide (Zr(CH 3 CH 2 )Br 3 ), isobutyl zirconium tribromide (Zr(i-C 4 h 9 )Br 3 ), n-butyl zirconium tribromide (Zr(C 4 h 9 )Br 3 );

[0143] Trimethylhafnium chloride (HfCl(CH 3 ) 3 ), triethyl hafnium chloride (HfCl(CH 3 CH 2 ) 3 ), triisobutyl hafnium chloride (HfCl(i-C 4 h 9 ) 3 ), tri-n-butyl hafnium chloride (HfCl(C 4 h 9 ) 3 ), dimethyl hafnium dichloride (HfCl 2 (CH 3 ) 2 ), diethyl hafnium dichloride (HfCl 2 (CH 3 CH 2 ) 2 ), diisobutyl hafnium dichloride (HfCl 2 (i-C 4 h 9 ) 2 ), tri-n-butyl hafnium chloride (HfCl(C 4 h 9 ) 3 ), methyl hafnium trichloride (Hf(CH 3 ) Cl 3 ), ethyl hafnium trichloride (Hf(CH 3 CH 2 ) Cl 3 ), isobutyl hafnium trichloride (Hf(i-C 4 h 9 ) Cl 3 ), n-butyl hafnium trichloride (Hf(C 4 h 9 ) Cl 3 );

[0144] Trimethylhafnium bromide (HfBr(CH 3 ) 3 ), triethyl hafnium bromide (HfBr(CH 3 CH 2 ) 3 ), triisobutyl hafnium bromide (HfBr(i-C 4 h 9 ) 3 ), tri-n-butyl hafnium bromide (HfBr(C 4 h 9 ) 3 ), dimethyl hafnium dibromide (HfBr 2 (CH 3 ) 2 ), diethyl hafnium dibromide (HfBr 2 (CH 3 CH 2 ) 2 ), diisobutyl hafnium dibromide (HfBr 2 (i-C 4 h 9 ) 2 ), tri-n-butyl hafnium bromide (HfBr(C 4 h 9 ) 3 ), methyl hafnium tribromide (Hf(CH 3 )Br 3 ), ethyl hafnium tribromide (Hf(CH 3 CH 2 )Br 3 ), isobutyl hafnium tribromide (Hf(i-C 4 h 9 )Br 3 ), n-butyl hafnium tribromide (Hf(C 4 h 9 )Br 3 ).

[0145] As the group IV B metal alkoxy halides, for example, titanium trimethoxychloride (TiCl(OCH 3 ) 3 ), titanium triethoxychloride (TiCl(OCH 3 CH 2 ) 3 ), triisobutoxytitanium chloride (TiCl(i-OC 4 h 9 ) 3 ), tri-n-butoxytitanium chloride (TiCl(OC 4 h 9 ) 3 ), dimethoxytitanium dichloride (TiCl 2 (OCH 3 ) 2 ), diethoxy titanium dichloride (TiCl 2 (OCH 3 CH 2 ) 2 ), diisobutoxytitanium dichloride (TiCl 2 (i-OC 4 h 9 ) 2 ), tri-n-butoxytitanium chloride (TiCl(OC 4 h 9 ) 3 ), methoxytitanium trichloride (Ti(OCH 3 ) Cl 3 ), ethoxylated titanium trichloride (Ti(OCH 3 CH 2 ) Cl 3 ), isobutoxytitanium trichloride (Ti(i-C 4 h 9 ) Cl 3 ), n-butoxytitanium trichloride (Ti(OC 4 h 9 ) Cl 3 );

[0146] Trimethoxytitanium bromide (TiBr(OCH 3 ) 3 ), triethoxytitanium bromide (TiBr(OCH 3 CH 2 ) 3 ), triisobutoxytitanium bromide (TiBr(i-OC 4 h 9 ) 3 ), tri-n-butoxytitanium bromide (TiBr(OC 4 h 9 ) 3 ), dimethoxytitanium dibromide (TiBr 2 (OCH 3 ) 2 ), diethoxytitanium dibromide (TiBr 2 (OCH 3 CH 2 ) 2 ), diisobutoxytitanium dibromide (TiBr 2 (i-OC 4 h 9 ) 2 ), tri-n-butoxytitanium bromide (TiBr(OC 4 h 9 ) 3 ), methoxytitanium tribromide (Ti(OCH 3 )Br 3 ), ethoxylated titanium tribromide (Ti(OCH 3 CH 2 )Br 3 ), isobutoxytitanium tribromide (Ti(i-C 4 h 9 )Br 3 ), n-butoxytitanium tribromide (Ti(OC 4 h 9 )Br 3 );

[0147] Trimethoxyzirconium chloride (ZrCl(OCH 3 ) 3 ), triethoxyzirconium chloride (ZrCl(OCH 3 CH 2 ) 3 ), triisobutoxyzirconium chloride (ZrCl(i-OC 4 h 9 ) 3 ), tri-n-butoxyzirconium chloride (ZrCl(OC 4 h 9 ) 3 ), dimethoxyzirconium dichloride (ZrCl 2 (OCH 3 ) 2 ), diethoxy zirconium dichloride (ZrCl 2 (OCH 3 CH 2 ) 2 ), diisobutoxyzirconium dichloride (ZrCl 2 (i-OC 4 h 9 ) 2 ), tri-n-butoxyzirconium chloride (ZrCl(OC 4 h 9 ) 3 ), methoxyzirconium trichloride (Zr(OCH 3 ) Cl 3 ), ethoxylated zirconium trichloride (Zr(OCH 3 CH 2 )Cl 3 ), isobutoxyzirconium trichloride (Zr(i-C 4 h 9 )Cl 3 ), n-butoxyzirconium trichloride (Zr(OC 4 h 9 )Cl 3 );

[0148] Trimethoxyzirconium bromide (ZrBr(OCH 3 ) 3 ), triethoxyzirconium bromide (ZrBr(OCH 3 CH 2 ) 3 ), triisobutoxyzirconium bromide (ZrBr(i-OC 4 h 9 ) 3 ), tri-n-butoxy zirconium bromide (ZrBr(OC 4 h 9 ) 3 ), dimethoxy zirconium dibromide (ZrBr 2 (OCH 3 ) 2 ), diethoxy zirconium dibromide (ZrBr 2 (OCH 3 CH 2 ) 2), diisobutoxy zirconium dibromide (ZrBr 2 (i-OC 4 h 9 ) 2 ), tri-n-butoxy zirconium bromide (ZrBr(OC 4 h 9 ) 3 ), methoxy zirconium tribromide (Zr(OCH 3 )Br 3 ), ethoxylated zirconium tribromide (Zr(OCH 3 CH 2 )Br 3 ), isobutoxy zirconium tribromide (Zr(i-C 4 h 9 )Br 3 ), n-butoxy zirconium tribromide (Zr(OC 4 h 9 )Br 3 );

[0149] Hafnium trimethoxychloride (HfCl(OCH 3 ) 3 ), hafnium triethoxychloride (HfCl(OCH 3 CH 2 ) 3 ), triisobutoxy hafnium chloride (HfCl(i-OC 4 h 9 ) 3 ), tri-n-butoxy hafnium chloride (HfCl(OC 4 h 9 ) 3 ), dimethoxyhafnium dichloride (HfCl 2 (OCH 3 ) 2 ), diethoxy hafnium dichloride (HfCl 2 (OCH 3 CH 2 ) 2 ), diisobutoxy hafnium dichloride (HfCl 2 (i-OC 4 h 9 ) 2 ), tri-n-butoxy hafnium chloride (HfCl(OC 4 h 9 ) 3 ), methoxyhafnium trichloride (Hf(OCH 3 )Cl 3 ), ethoxy hafnium trichloride (Hf(OCH 3 CH 2 )Cl 3 ), isobutoxy hafnium trichloride (Hf(i-C 4 h 9 )Cl 3 ), n-butoxy hafnium trichloride (Hf(OC 4 h 9 )Cl 3 );

[0150] Hafnium trimethoxybromide (HfBr(OCH 3 ) 3 ), triethoxy hafnium bromide (HfBr(OCH 3 CH 2 ) 3 ), triisobutoxy hafnium bromide (HfBr(i-OC 4 h 9 ) 3 ), tri-n-butoxy hafnium bromide (HfBr(OC 4 h 9 ) 3 ), hafnium dimethoxydibromide (HfBr 2 (OCH 3 ) 2 ), diethoxy hafnium dibromide (HfBr 2 (OCH 3 CH 2 ) 2 ), diisobutoxy hafnium dibromide (HfBr 2 (i-OC 4 h 9 ) 2 ), tri-n-butoxy hafnium bromide (HfBr(OC 4 h 9 ) 3 ), Methoxy hafnium tribromide (Hf(OCH 3 )Br 3 ), ethoxy hafnium tribromide (Hf(OCH 3 CH 2 )Br 3 ), isobutoxy hafnium tribromide (Hf(i-C 4 h 9 )Br 3 ), n-butoxy hafnium tribromide (Hf(OC 4 h 9 )Br 3 ).

[0151] As the IV B group metal compound, preferably the IV B group metal halide, more preferably TiCl 4 、TiBr 4 , ZrCl 4 , ZrBr 4 , HfCl 4 and HfBr 4 , most preferably TiCl 4 and ZrCl 4.

[0152] One of these Group IV B metal compounds may be used alone, or a plurality of them may be used in combination in an arbitrary ratio.

[0153] When the chemical treatment agent is liquid at normal temperature, the chemical treatment agent can be directly used to carry out the chemical treatment reaction. When the chemical treatment agent is solid at normal temperature, it is preferable to use the chemical treatment agent in the form of a solution for the convenience of metering and operation. Of course, when the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment agent may sometimes be used in the form of a solution if necessary, and there is no particular limitation.

[0154] When 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 (such as dissolve) the existing magnesium compound or the modified carrier. carrier structure.

[0155] Specifically, one can cite C 5-12 Alkanes, C 5-12 Cycloalkanes, halogenated C 5-12 Alkanes and halogenated C 5-12 Cycloalkanes, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, Chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane and chlorocyclohexane, among which Preferred are pentane, hexane, decane and cyclohexane, most preferably hexane.

[0156] These solvents may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0157] In addition, the concentration of the chemical treatment agent in its solution is not particularly limited, and can be appropriately selected according to needs, as long as it can realize the chemical treatment reaction with a predetermined amount of the chemical treatment agent. As mentioned above, if the chemical treatment agent is in a liquid state, the chemical treatment agent can be used directly for the treatment, but it can also be used after being prepared as a solution of the chemical treatment agent.

[0158] Generally speaking, the molar concentration of the chemical treatment agent in its solution is generally set at 0.01˜1.0 mol/L, but it is not limited thereto.

[0159] As the method for carrying out the chemical treatment, for example, in the case of using a solid chemical treatment agent (such as zirconium tetrachloride), first prepare a solution of the chemical treatment agent, and then apply the chemical treatment agent to the modified carrier to be treated Add (preferably drop) a predetermined amount of the chemical treatment agent; in the case of using a liquid chemical treatment agent (such as titanium tetrachloride), the predetermined amount of the chemical treatment agent can be directly (but also after being prepared into a solution) The chemical treatment agent is added (preferably dropwise) to the modified carrier to be treated, and the chemical treatment reaction (with stirring if necessary) is carried out for 0.5 ~24h, preferably 1~8h, more preferably 2~6h, then filter, wash and dry.

[0160] According to the present invention, the filtering, washing and drying can be carried out by conventional methods, and the washing solvent can be the same solvent as that used for dissolving the chemical treatment agent. This washing is generally performed 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times.

[0161] According to the present invention, as the consumption of the chemical treatment agent, the molar ratio of the magnesium compound (solid) in terms of Mg element to the chemical treatment agent in terms of IV Group B metal (such as Ti) element reaches 1: 0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

[0162] According to a particular embodiment of the present invention, the preparation method of the magnesium single-carrier in-situ supported non-metallocene catalyst of the present invention also includes, before using the chemical treatment agent to treat the modified carrier, using a compound selected from aluminoxane, alkane The step of pretreating the modified support with an auxiliary chemical treatment agent based on aluminum or any combination thereof (pretreatment step). Then, carry out the chemical treatment with the chemical treatment agent in exactly the same manner as above, except that the modified carrier is replaced by the pretreated modified carrier.

[0163] The auxiliary chemical treatment agent will be described in detail below.

[0164] According to the present invention, examples of the auxiliary chemical treatment agent include aluminoxane and alkylaluminum.

[0165] As the aluminoxane, for example, a linear aluminoxane represented by the following general formula (I): (R)(R)Al-(Al(R)-O) n -O-Al(R)(R), and a cyclic aluminoxane represented by the following general formula (II): -(Al(R)-O-) n+2 -.

[0166]

[0167] In the aforementioned general formula, the groups R are the same or different (preferably the same) from each other, each independently selected from C 1 -C 8 Alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl; n is any integer within the range of 1-50, preferably any integer within the range of 10-30.

[0168] As the aluminoxane, methylalumoxane, ethylalumoxane, isobutylalumoxane and n-butylalumoxane are preferable, and methylalumoxane and isobutylalumoxane are more preferable.

[0169] These aluminoxanes may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0170] As the aluminum alkyl, for example, compounds represented by the following general formula (III):

[0171] Al(R) 3 (III)

[0172] Wherein, the groups R are the same or different (preferably the same) with each other, and are each independently selected from C 1 -C 8 Alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl.

[0173] Specifically, examples of the alkylaluminum include trimethylaluminum (A1(CH 3 ) 3 ), triethylaluminum (Al(CH 3 CH 2 )3 ), tripropylaluminum (Al(C 3 h 7 ) 3 ), triisobutylaluminum (Al(i-C 4 h 9 ) 3 ), tri-n-butylaluminum (Al(C 4 h 9 ) 3 ), triisopentylaluminum (A1(i-C 5 h 11 ) 3 ), tri-n-pentyl aluminum (Al(C 5 h 11 ) 3 ), trihexyl aluminum (Al(C 6 h 13 ) 3 ), triisohexyl aluminum (Al(i-C 6 h 13 ) 3 ), diethylmethylaluminum (A1(CH 3 )(CH 3 CH 2 ) 2 ) and dimethylethylaluminum (Al(CH 3 CH 2 )(CH 3 ) 2 ), etc., wherein trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferred, and triethylaluminum and triisobutylaluminum are most preferred.

[0174] These alkylaluminums may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0175] According to the present invention, as the auxiliary chemical treatment agent, only the aluminoxane or the aluminum alkyl can be used, but any mixture of the aluminoxane and the aluminum alkyl can also be used. Moreover, the ratio of each component in the mixture is not particularly limited, and can be arbitrarily selected according to needs.

[0176] According to the present invention, the auxiliary chemical treatment agent is generally used in the form of a solution. When preparing the solution of the auxiliary chemical treatment agent, the solvent used at this time is not particularly limited, as long as it can dissolve the auxiliary chemical treatment agent and does not destroy (such as dissolve) the existing carrier structure of the carrier .

[0177] Specifically, as the solvent, for example, C 5-12 Alkanes and halogenated C 5-12 Alkanes, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, chloropentane, chlorohexane, chloroheptane alkane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane and chlorocyclohexane, among which pentane, hexane, decane and cyclohexane are preferred , most preferably hexane.

[0178] These solvents may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0179] In addition, the concentration of the auxiliary chemical treatment agent in its solution is not particularly limited, and can be appropriately selected according to needs, as long as it can realize the pretreatment with a predetermined amount of the auxiliary chemical treatment agent.

[0180] As the method for carrying out the pretreatment, for example, the solution of the auxiliary chemical treatment agent is firstly prepared, and then at a temperature of -30 to 60°C (preferably -20 to 30°C), the Metering (preferably dropwise) the auxiliary chemical treatment agent solution (containing a predetermined amount of the auxiliary chemical treatment agent) into the modified carrier pretreated by the auxiliary chemical treatment agent, or metering the auxiliary chemical treatment agent solution into the described auxiliary chemical treatment agent solution The carrier is modified as described above to form a reaction mixture, which is allowed to react for 1-8 hours, preferably 2-6 hours, most preferably 3-4 hours (stirring is used if necessary). Then, the obtained pretreated product is separated from the reaction mixture by filtering, washing (1 to 6 times, preferably 1 to 3 times) and optionally drying, or can be obtained without the separation as The form of the mixed solution was directly used in the subsequent reaction step. At this point, since the mixed solution already contains a certain amount of solvent, the amount of solvent involved in the subsequent reaction step can be correspondingly reduced.

[0181] According to the present invention, as the amount of the auxiliary chemical treatment agent, the molar ratio of the magnesium compound (solid) in terms of Mg element to the described auxiliary chemical treatment agent in terms of Al element reaches 1:0-1.0, preferably 1:0-0.5, more preferably 1:0.1-0.5.

[0182] It is known to those skilled in the art that all the aforementioned process steps are preferably carried out under substantially anhydrous and oxygen-free conditions. The term “substantially anhydrous and oxygen-free” here means that the content of water and oxygen in the system is continuously less than 10ppm. Moreover, the magnesium single carrier in situ supported non-metallocene catalyst of the present invention usually needs to be stored under a slightly positive pressure under airtight conditions after preparation.

[0183] According to the present invention, as the amount of the non-metallocene ligand used, the molar ratio of the magnesium compound (solid) in terms of Mg element to the non-metallocene ligand reaches 1:0.0001-1, preferably 1:0.0002 -0.4, more preferably 1:0.0008-0.2, still more preferably 1:0.001-0.1.

[0184] According to the present invention, the amount of tetrahydrofuran used to dissolve the magnesium compound is such that the ratio of the magnesium compound (solid) to tetrahydrofuran is 1mol: 0.5-10L, preferably 1mol: 1-8L, more preferably 1mol: 2-6L .

[0185] According to the present invention, as the consumption of the chemical treatment agent, the molar ratio of the magnesium compound (solid) in terms of Mg element to the chemical treatment agent in terms of IV Group B metal (such as Ti) element reaches 1: 0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

[0186] According to the present invention, as the amount of the auxiliary chemical treatment agent, the molar ratio of the magnesium compound (solid) in terms of Mg element to the described auxiliary chemical treatment agent in terms of Al element reaches 1:0-1.0, preferably 1:0-0.5, more preferably 1:0.1-0.5.

[0187] According to the present invention, as the amount of the precipitant, the volume ratio of the precipitant to the tetrahydrofuran used to dissolve the magnesium compound is 1:0.2~5, preferably 1:0.5~2, more preferably 1:0.8~ 1.5.

[0188] In one embodiment, the present invention also relates to a supported non-metallocene catalyst (sometimes also referred to as a supported non-metallocene olefin polymerization catalyst) produced by the aforementioned method for preparing a magnesium single-carrier in-situ supported non-metallocene catalyst.

[0189] In a further embodiment, the present invention relates to a method for homopolymerization/copolymerization of olefins, wherein the magnesium single carrier in-situ supported non-metallocene catalyst of the present invention is used as a catalyst for olefin polymerization to homopolymerize or copolymerize olefins.

[0190] As far as the olefin homopolymerization/copolymerization method involved in the present invention is concerned, except for the content specified below, other unspecified content (such as polymerization reactor, olefin dosage, catalyst and olefin addition method, etc.) can be directly Those conventionally known in the art are applicable without particular limitation, and descriptions thereof are omitted here.

[0191] According to the homopolymerization/copolymerization method of the present invention, the magnesium single carrier in-situ supported non-metallocene catalyst of the present invention is used as the main catalyst, and the catalyst is selected from the group consisting of aluminoxane, aluminum alkyl, aluminum halide, fluoroalkyl, alkyl One or more of boron and alkyl boron ammonium salts are cocatalysts to homopolymerize or copolymerize olefins.

[0192] The method of adding the main catalyst and the co-catalyst to the polymerization reaction system can be to add the main catalyst first, and then add the co-catalyst, or add the co-catalyst first, and then add the main catalyst, or the two are first contacted and mixed and then added together, or join at the same time. When the main catalyst and co-catalyst are added separately, they can be added sequentially in the same feeding pipeline, or can be added sequentially in multiple feeding pipelines. When the two are added at the same time, multiple feeding pipelines should be selected. For continuous polymerization, it is preferred that multiple feeding pipelines be added continuously at the same time, while for batch polymerization, it is preferred that the two be mixed first and then added together in the same feeding pipeline, or in the same feeding pipeline first The cocatalyst is added followed by the main catalyst.

[0193] According to the present invention, the reaction mode of the olefin homopolymerization/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, etc., Among them, the slurry method and the gas phase method are preferable.

[0194] According to the present invention, as the olefin, for example, C 2 ~C 10 Mono-olefins, di-olefins, cyclic olefins and other ethylenically unsaturated compounds.

[0195] Specifically, as the C 2 ~C 10 Monoolefins, such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-undecene ene, 1-dodecene, styrene, etc.; as the cyclic olefin, for example, 1-cyclopentene and norbornene, etc. can be mentioned; as the diolefin, for example, 1,4-butanediene can be mentioned ene, 2,5-pentadiene, 1,6-hexadiene, norbornadiene, 1,7-octadiene, etc.; and as said other ethylenically unsaturated compounds, for example, vinyl acetate esters and (meth)acrylates, etc. Among them, homopolymerization of ethylene or copolymerization of ethylene with propylene, 1-butene or 1-hexene is preferable.

[0196] According to the present invention, homopolymerization refers to the polymerization of only one said olefin, while copolymerization refers to the polymerization between two or more said olefins.

[0197] According to the present invention, the cocatalyst is selected from the group consisting of aluminoxanes, aluminum alkyls, alkylaluminum halides, borofluorocarbons, boron alkyls and ammonium boron salts, among which aluminoxanes and aluminum alkyls are preferred.

[0198] As the aluminoxane, for example, a linear aluminoxane represented by the following general formula (I-1): (R)(R)Al-(Al(R)-O) n -O-Al(R)(R), and a cyclic aluminoxane represented by the following general formula (II-1): -(Al(R)-O-) n+2 -.

[0199]

[0200] In the aforementioned general formula, the groups R are the same or different (preferably the same) from each other, each independently selected from C 1 -C 8 Alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl; n is any integer within the range of 1-50, preferably any integer within the range of 10-30.

[0201] As the aluminoxane, methylalumoxane, ethylalumoxane, isobutylalumoxane and n-butylalumoxane are preferred, methylalumoxane and isobutylalumoxane are more preferred, and most Methylalumoxane is preferred.

[0202] These aluminoxanes may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0203] As the alkylaluminum, for example, compounds represented by the following general formula (III-1):

[0204] Al(R) 3 (III-1)

[0205] Wherein, the groups R are the same or different (preferably the same) with each other, and are each independently selected from C 1 -C 8 Alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl.

[0206] Specifically, examples of the alkylaluminum include trimethylaluminum (Al(CH 3 ) 3 ), triethylaluminum (Al(CH 3 CH 2 ) 3 ), tripropylaluminum (Al(C 3 h 7 ) 3 ), triisobutylaluminum (Al(i-C 4 h 9 ) 3 ), tri-n-butylaluminum (Al(C 4 h 9 ) 3 ), triisopentylaluminum (Al(i-C 5 h 11 ) 3 ), tri-n-pentyl aluminum (Al(C 5 h 11 ) 3 ), trihexyl aluminum (Al(C 6 h 13 ) 3 ), triisohexyl aluminum (Al(i-C 6 h 13 ) 3 ), diethylmethylaluminum (Al(CH 3 )(CH 3 CH 2 ) 2 ) and dimethylethylaluminum (Al(CH 3 CH 2 )(CH 3 ) 2 ), etc., among which trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferred, triethylaluminum and triisobutylaluminum are further preferred, and triethylaluminum is most preferred.

[0207] These alkylaluminums may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0208] As the haloalkylaluminum, the borofluoroane, the alkylboron, and the alkylboronammonium salt, those conventionally used in the art can be directly used without any particular limitation.

[0209] In addition, according to the present invention, one kind of the co-catalyst can be used alone, or a plurality of the aforementioned co-catalysts can be used in combination in any ratio as required, and there is no special limitation.

[0210] According to the present invention, depending on the reaction mode of the olefin homopolymerization/copolymerization method, sometimes it is necessary to use a polymerization solvent.

[0211] As the polymerization solvent, those conventionally used in the art for olefin homopolymerization/copolymerization may be used without particular limitation.

[0212] As the polymerization solvent, for example, C 4-10 Alkanes (such as butane, pentane, hexane, heptane, octane, nonane or decane, etc.), halogenated C 1-10 Alkanes (such as methylene chloride), aromatic hydrocarbon solvents (such as toluene and xylene), ether solvents (such as diethyl ether or tetrahydrofuran), ester solvents (such as ethyl acetate), and ketone solvents (such as acetone), etc. Among them, hexane is preferably used as the polymerization solvent.

[0213] These polymerization solvents may be used alone or in combination of a plurality of them in an arbitrary ratio.

[0214] According to the present invention, the polymerization reaction pressure of the olefin homopolymerization/copolymerization method is generally 0.1-10 MPa, preferably 0.1-4 MPa, more preferably 1-3 MPa, but sometimes it is not limited thereto. According to the present invention, the polymerization reaction temperature is generally -40°C to 200°C, preferably 10°C to 100°C, more preferably 40°C to 90°C, but sometimes it is not limited thereto.

[0215] In addition, according to the present invention, the olefin homopolymerization/copolymerization method can be carried out in the presence of hydrogen or in the absence of hydrogen. When present, the partial pressure of hydrogen may be 0.01% to 99% of the polymerization reaction pressure, preferably 0.01% to 50%, but sometimes it is not limited thereto.

[0216] According to the present invention, when carrying out the olefin homopolymerization/copolymerization method, the molar ratio of the cocatalyst in aluminum or boron to the magnesium single carrier in-situ supported non-metallocene catalyst in IV B group metal Generally, it is 1:1-1000, preferably 1:1-500, more preferably 1:10-500, but sometimes it is not limited thereto.

[0226] Example 1

[0227] Weigh 2.5g magnesium compound anhydrous magnesium chloride (MgCl 2 ), add a certain amount of tetrahydrofuran, heat to 60 ° C to dissolve, add a certain amount of non-metallocene ligands, continue stirring at 60 ° C to dissolve completely, and obtain a magnesium compound solution. After stirring for 2 hours, add a precipitant hexane to make it precipitate , filtered, and the solid product was collected, washed twice with hexane, and the amount of hexane added each time was the same as that added before, and the obtained solid product was dried at 45 °C and an absolute pressure of 10 mBar for 6 h, and then at 80 °C and Drying under a vacuum of 10 mBar for 8 hours obtained a modified carrier, wherein the tetrahydrofuran content was 0.17 wt%.

[0228] Measure 25ml of hexane solvent, join in the modified carrier, add titanium tetrachloride (TiCl) dropwise in 15 minutes under stirring condition 4 ) the hexane solution of the chemical treatment agent, after reacting at 30°C for 4h, filter, wash with hexane 3 times, 25ml each time, and finally vacuum-dry at 30°C and absolute pressure 10mBar for 12h to obtain the in-situ loading of magnesium single carrier non-metallocene catalysts.

[0229] Wherein: non-metallocene ligand adopts structural formula as compound of.

[0230] The ratio is: the ratio of magnesium compound to tetrahydrofuran is 1mol:4L; the molar ratio of magnesium compound to non-metallocene ligand is 1:0.004; the volume ratio of precipitant hexane to tetrahydrofuran is 1:1; magnesium compound and chemical treatment agent The molar ratio of titanium tetrachloride is 1:0.20.

[0231] This catalyst is designated CAT-1.

[0232] Example 2

[0233] Basically the same as Example 1, but with the following changes:

[0234] Without using a precipitating agent, the magnesium compound solution was dried at 35° C. and an absolute pressure of 10 mBar under vacuum for 10 h, and then at 90° C. and an absolute pressure of 10 mBar under vacuum for 6 h to obtain a modified carrier, wherein the tetrahydrofuran content was 0.13 wt%.

[0235] This catalyst is designated CAT-2.