A non-metallocene catalyst and its preparation method and application

Abstract

The application discloses a non-metallocene catalyst and a preparation method and application thereof. The non-metallocene catalyst has the following formula I structure: wherein M is selected from group IVB transition metal atoms; L is a halogen atom; X is selected from one of O, NH and S; R1, R2 and R3 are independently selected from hydrogen, a substituted or unsubstituted aliphatic group with 1-12 carbons, a substituted or unsubstituted aromatic group with 6-12 carbons, an oxygen-containing group, a sulfur-containing group or a halogen atom, and R2 and R3 can also be selected from a nitrogen-containing group; or R3 is selected from hydrogen, a substituted or unsubstituted aliphatic group with 1-12 carbons, a substituted or unsubstituted aromatic group with 6-12 carbons, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a halogen atom, and R1 and R2 form a cyclic structure and are a substituted or unsubstituted C4-C8 conjugated olefin group; and n is 1-3. The non-metallocene catalyst has high polymerization activity in olefin polymerization and can be used to prepare low-molecular-weight polyethylene.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a non-metallocene catalyst, its preparation method, and its application. Background Technology

[0002] In the development of olefin polymerization catalysts, non-metallocene catalysts, developed in the 1990s, have received significant attention and development. Because they emerged after metallocene catalysts, they are sometimes referred to as "post-metallocene" olefin polymerization catalysts. They possess characteristics similar to metallocene catalysts, allowing for the customization of polymers to meet specific needs, and are also less expensive. The central atoms of non-metallocene catalysts include almost all transition metal elements, and in some performance aspects, they have reached or even surpassed those of metallocene catalysts, becoming a new generation of olefin polymerization catalysts following Ziegler-Natta and metallocene catalysts.

[0003] Based on the different central atoms of the main catalyst, catalysts can be further classified into non-metallocene pre-transition metal (Group IIIB, IVB, VB, VIB, VIIB) catalysts and non-metallocene post-transition metal (Group VIII) catalysts. Polyolefin products manufactured using these catalysts exhibit excellent performance and low manufacturing costs. Non-metallocene catalysts have oxygen, nitrogen, sulfur, and phosphorus as coordinating atoms, and do not contain cyclopentadienyl groups or their derivatives, such as indenyl and fluorenyl groups. Their characteristics include a strong electrophilic central ion and a cis-alkyl or halide metal central structure, facilitating olefin insertion. The central metal is easily alkylated, which is beneficial for the formation of cationic active centers. The resulting complexes have defined geometric configurations, and their stereoselectivity, electronegativity, and chirality are adjustable. Furthermore, the formed metal-carbon bonds are easily polarized, further promoting olefin polymerization and copolymerization. Therefore, high polymerization activity can be obtained at the polymerization reaction temperature. In particular, group IV transition metal complexes containing phenoxy-imine ligands (EP0874005, W00155231) have high catalytic activity for olefin polymerization and can produce polyolefin resins with functionalization and other characteristics.

[0004] Patents ZL01126323.7, ZL02151294.9, ZL02110844.7, and WO 03 / 010207 disclose an olefin homopolymerization / copolymerization catalyst or catalytic system with broad olefin homopolymerization / copolymerization properties. However, the catalysts or catalytic systems disclosed in these patents require a high amount of co-catalyst to obtain suitable olefin polymerization activity during olefin polymerization, and the polymerization process suffers from short activity duration and polymer sticking to the reactor. Patent CN102295714 discloses an ethylene polymerization catalyst, which catalyzes polyethylene with a molecular weight of over 1 million.

[0005] Therefore, further research on non-metallocene catalysts is needed in this field. Summary of the Invention

[0006] The main objective of this invention is to provide a non-metallocene catalyst, its preparation method, and its application, so as to overcome the defects of high co-catalyst dosage and low activity of non-metallocene catalysts in the olefin polymerization process of the prior art.

[0007] To achieve the above objectives, the present invention provides a non-metallocene catalyst having the following structure: Formula I:

[0008]

[0009] Wherein, M is selected from Group IVB transition metal atoms;

[0010] L represents a halogen atom;

[0011] X is selected from one of O, NH and S;

[0012] R1 is selected from hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbons, an oxygen-containing group, a sulfur-containing group, or a halogen atom; R2 and R3 are independently selected from hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbons, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a halogen atom; or, R3 is selected from hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbons, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a halogen atom; R1 and R2 form a cyclic structure and are substituted or unsubstituted C4 to C8 conjugated olefin groups;

[0013] n is 1 to 3.

[0014] In one embodiment of the non-metallocene catalyst of the present invention, R1, R2 and R3 are not all hydrogen.

[0015] In one embodiment of the non-metallocene catalyst of the present invention, M is Ti, Zr, or Hf; L is Cl or Br; n is 2; R1 is selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms; R2 and R3 are independently selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, or alkylthio groups having 1 to 12 carbons. R1 and R2 form a cyclic structure and are unsubstituted C4-C8 conjugated alkenes or C4-C8 conjugated alkenes containing alkoxy or alkylthio groups. R3 is selected from an aliphatic hydrocarbon group having 1-12 carbons, an aromatic hydrocarbon group having 6-12 carbons, an alkoxy group having 1-12 carbons, an alkoxy group having 1-12 carbons, an alkylamine group having 1-12 carbons, a nitro group, or a halogen atom. R1 and R2 form a cyclic structure and are unsubstituted C4-C8 conjugated alkenes or C4-C8 conjugated alkenes containing alkoxy or alkoxy substituents.

[0016] In one embodiment, the non-metallocene catalyst of the present invention has one of the following structures:

[0017] 1. M=Ti, X=O, n=2, L=Cl, R1=OCH3, R2=H, R3=CH3;

[0018] 2. M=Ti, X=O, n=2, L=Cl, R1=OCH3, R2=R3=H;

[0019] 3. M=Ti, X=O, n=2, L=Cl, R1=t-Bu, R2=H, R3=OCH3;

[0020] 4. M=Ti, X=O, n=2, L=Cl, R1=i-OPr, R2=R3=H;

[0021] 5. M=Ti, X=O, n=2, L=Cl, R1=n-OBu, R2=R3=H;

[0022] 6. M=Ti, X=O, n=2, L=Cl, R1=Br, R2=H, R3=Cl;

[0023] 7. M=Ti, X=O, n=2, L=Br, R1=t-Bu, R2=H, R3=OCH3;

[0024] 8. M=Ti, X=NH, n=2, L=Cl, R1=OCH3, R2=R3=H;

[0025] 9. M=Ti, X=O, n=2, L=Cl, R1=SCH3, R2=R3=H;

[0026] 10. M=Ti, X=NH, n=2, L=Cl, R1=-OBu, R2=R3=H;

[0027] 11. M = Ti, X = O, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-CH = CH-, R3 = H;

[0028] 12. M = Ti, X = O, n = 2, L = Cl, R1 and R2 form a ring and are -CH = C(OCH3)-CH = CH-, R3 = H;

[0029] 13. M = Ti, X = NH, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-CH = CH-, R3 = H;

[0030] 14. M = Ti, X = NH, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-C(OCH3) = CH-, R3 = H;

[0031] 15. M=Ti, X=O, n=2, L=Cl, R1=Cl, R2=R3=H;

[0032] 16. M=Ti, X=O, n=2, L=Cl, R1=Cl, R2=H, R3=CH3;

[0033] 17. M = Ti, X = S, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-CH = CH-, R3 = H;

[0034] 18. M = Ti, X = NH, n = 2, L = Cl, R1 and R2 form a ring and are -CH = C(OCH3) - C(OCH3) = CH-, R3 = H;

[0035] 19. M = Ti, X = O, n = 2, L = Cl, R1 and R2 form a ring and are -CH = C(OCH3) - C(OCH3) = CH-, R3 = H.

[0036] To achieve the above objectives, the present invention also provides a method for preparing a non-metallocene catalyst, comprising the following steps:

[0037] Step 1: Mix the transition metal compound with the aryl ligand and react at 50℃~120℃;

[0038] Step 2: Cool the mixture obtained in Step 1 to 0℃~30℃ and continue the reaction in an inert gas environment;

[0039] Step 3: The mixture obtained in Step 2 is post-processed and dried to obtain a non-metallocene catalyst;

[0040] Wherein, the transition metal compound is a compound of a Group IVB transition metal, and the aryl ligand is an arylphenol, aryl sulfide, or arylamine with or without substituents.

[0041] In one embodiment of the preparation method of the non-metallocene catalyst of the present invention, the transition metal compound is a compound of Ti, Zr or Hf, and the substituent is selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbons, oxygen-containing group, sulfur-containing group or halogen atom.

[0042] In one embodiment of the preparation method of the non-metallocene catalyst of the present invention, the transition metal compound is a chloride of Ti, Zr or Hf, and the substituent is selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms.

[0043] In one embodiment of the method for preparing the non-metallocene catalyst of the present invention, the aryl ligand contains at least two substituents located on adjacent carbons of the aromatic ligand, and the at least two substituents form a cyclic structure, which are substituted or unsubstituted C4-C8 conjugated olefin groups.

[0044] In one embodiment of the method for preparing the non-metallocene catalyst of the present invention, the at least two substituents form a cyclic structure and are unsubstituted C4-C8 conjugated olefin groups, or C4-C8 conjugated olefins containing alkoxy substituents, alkylthio substituents, or halogen substituents.

[0045] In one embodiment of the preparation method of the non-metallocene catalyst of the present invention, the transition metal compound and the aryl ligand are dissolved separately in an organic solvent and then mixed. The organic solvent is selected from C4 to C5. 10 Alkanes, halogenated C1-C 10 Alkanes, C6-C 10 Cycloalkanes or C6-C 20 Aromatic hydrocarbons.

[0046] To achieve the above objectives, the present invention further provides an olefin polymerization method, using the aforementioned non-metallocene catalyst as the main catalyst.

[0047] In one embodiment of the olefin polymerization method of the present invention, organoaluminum is used as a co-catalyst.

[0048] The beneficial effects of this invention are:

[0049] The non-metallocene catalyst of this invention can be used for olefin polymerization, and can exhibit high catalytic activity with a small amount of co-catalyst, reaching 3-6 kg PE (g·cat·h). -1 This method can produce low molecular weight polyethylene, for example, with a viscosity-average molecular weight of 8675-12586 g / mol, and the resulting polymer has good morphology, crystallinity of 59-78%, and molecular weight distribution of 2-5.

[0050] The non-metallocene catalyst of this invention uses readily available raw materials, is low in cost, has a simple preparation process, is easy to operate, and is suitable for industrial production.

[0051] Instruction manual illustrations

[0052] Figure 1 The image shows the carbon NMR spectrum of catalyst CAT-1 in Example 1 of this invention.

[0053] Figure 2 This is the carbon NMR spectrum of catalyst CAT-4 in Example 4 of the present invention. Detailed Implementation

[0054] The following provides a detailed description of the embodiments of the present invention. These embodiments are implemented based on the technical solution of the present invention and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0055] This invention provides a non-metallocene catalyst having the following structure: Formula I:

[0056]

[0057] It should be noted that in Formula I, n represents the group connected to M. The quantity, for example, if n is 2, then it represents two. The groups are bonded to M respectively; similarly, 4-n represents the number of groups L bonded to M. For example, if n is 2, it means that two L groups are bonded to M respectively, thus obtaining the structure of Equation II as follows:

[0058]

[0059] Wherein, M is selected from transition metal atoms of Group III to Group XI, preferably transition metal atoms of Group IVB;

[0060] L represents a halogen atom;

[0061] X is selected from one of O, NH and S;

[0062] R1, R2, and R3 are independently selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, or halogen atoms. R2 and R3 may also be nitrogen-containing groups. Alternatively, R3 may be selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, or halogen atoms. R1 and R2 form a cyclic structure and are substituted or unsubstituted C4 to C8 conjugated olefin groups.

[0063] n is 1 to 3.

[0064] In one embodiment, M is Ti, Zr, or Hf; L is Cl or Br; n is 2; and R1, R2, and R3 are not all hydrogen. In another embodiment, R1, R2, and R3 are independently selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms. R2 and R3 can be nitrogen-containing groups, such as alkylamines or nitro groups having 1 to 12 carbons. Alternatively, R3 can be selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, alkylamines having 1 to 12 carbons, nitro groups, or halogen atoms. R1 and R2 form a cyclic structure and are unsubstituted C4 to C8 conjugated olefin groups or C4 to C8 conjugated olefin groups containing alkoxy or alkylthio substituents.

[0065] In another embodiment, the non-metallocene catalyst has one of the following structures:

[0066] 1. M=Ti, X=O, n=2, L=Cl, R1=OCH3, R2=H, R3=CH3;

[0067] 2. M=Ti, X=O, n=2, L=Cl, R1=OCH3, R2=R3=H;

[0068] 3. M=Ti, X=O, n=2, L=Cl, R1=t-Bu, R2=H, R3=OCH3;

[0069] 4. M=Ti, X=O, n=2, L=Cl, R1=i-OPr, R2=R3=H;

[0070] 5. M=Ti, X=O, n=2, L=Cl, R1=n-OBu, R2=R3=H;

[0071] 6. M=Ti, X=O, n=2, L=Cl, R1=Br, R2=H, R3=Cl;

[0072] 7. M=Ti, X=O, n=2, L=Br, R1=t-Bu, R2=H, R3=OCH3;

[0073] 8. M=Ti, X=NH, n=2, L=Cl, R1=OCH3, R2=R3=H;

[0074] 9. M=Ti, X=O, n=2, L=Cl, R1=SCH3, R2=R3=H;

[0075] 10. M=Ti, X=NH, n=2, L=Cl, R1=-OBu, R2=R3=H;

[0076] 11. M = Ti, X = O, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-CH = CH-, R3 = H, wherein R1 and R2 form a naphthalene ring structure with the benzene ring in Formula I;

[0077] 12. M = Ti, X = O, n = 2, L = Cl, R1 and R2 form a ring and are -CH = C(OCH3)-CH = CH-, R3 = H;

[0078] 13. M = Ti, X = NH, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-CH = CH-, R3 = H;

[0079] 14. M = Ti, X = NH, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-C(OCH3) = CH-, R3 = H;

[0080] 15. M=Ti, X=O, n=2, L=Cl, R1=Cl, R2=R3=H;

[0081] 16. M=Ti, X=O, n=2, L=Cl, R1=Cl, R2=H, R3=CH3;

[0082] 17. M = Ti, X = S, n = 2, L = Cl, R1 and R2 form a ring and are -CH = CH-CH = CH-, R3 = H;

[0083] 18. M = Ti, X = NH, n = 2, L = Cl, R1 and R2 form a ring and are -CH = C(OCH3) - C(OCH3) = CH-, R3 = H;

[0084] 19. M = Ti, X = O, n = 2, L = Cl, R1 and R2 form a ring and are -CH = C(OCH3) - C(OCH3) = CH-, R3 = H.

[0085] This invention also provides a method for preparing a non-metallocene catalyst, comprising the following steps:

[0086] Step 1: Mix the transition metal compound with the aryl ligand and react at 50℃~120℃;

[0087] Step 2: Cool the mixture obtained in Step 1 to 0℃~30℃ and continue the reaction in an inert gas environment;

[0088] Step 3: The mixture obtained in Step 2 is post-processed and dried to obtain a non-metallocene catalyst;

[0089] Wherein, the transition metal compound is a compound of a Group IVB transition metal, and the aryl ligand is an arylphenol, aryl sulfide, or arylamine with or without substituents.

[0090] In one embodiment, the non-metallocene catalyst of the present invention can be prepared according to the preparation method described above.

[0091] In another embodiment, the transition metal compound in the preparation method of the present invention is a compound of Ti, Zr or Hf. In yet another embodiment, the transition metal compound is a chloride of Ti, Zr or Hf, such as a tetrachloride of Ti, Zr or Hf.

[0092] In another embodiment, the aryl ligand contains substituents selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, or halogen atoms. In yet another embodiment, the substituents of the aryl ligand are selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, or halogen atoms. In still another embodiment, the aryl ligand contains at least two substituents located on adjacent carbons of the aromatic ligand, and the at least two substituents form a cyclic structure, which is a substituted or unsubstituted C4 to C8 conjugated olefin group. In yet another embodiment, the at least two substituents form a cyclic structure and are unsubstituted C4-C8 conjugated olefin groups, or C4-C8 conjugated olefin groups containing alkoxy substituents, alkylthio substituents, or halogen substituents; further, the substituents in the substituted C4-C8 conjugated olefin groups can be alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms. In yet another embodiment, the aryl group in the aryl ligand of the present invention is phenyl, naphthyl, etc.

[0093] In one embodiment, the transition metal compound and the aryl ligand of the present invention are dissolved separately in an organic solvent and then mixed. The organic solvent is selected from C4 to C5. 10 Alkanes, halogenated C1-C 10Alkanes, C6-C 10 Cycloalkanes or C6-C 20 Aromatic hydrocarbons. In another embodiment, the organic solvent is selected from butane, pentane, hexane, heptane, octane, nonane, decane, dichloromethane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, xylene, or other organic solvents, wherein n-hexane, n-heptane, and toluene are preferred, and toluene is most preferred.

[0094] In one embodiment, the molar ratio of the transition metal compound to the aryl ligand is 1:2.

[0095] In one specific embodiment, the preparation method of the non-metallocene catalyst of the present invention includes the following steps:

[0096] Step 1: Under stirring, the solution of the transition metal compound dissolved in the organic solvent is slowly added dropwise to the solution containing the aryl ligand at a temperature of 0℃~50℃, and refluxed at a constant temperature of 50℃~120℃ for 1h~4h.

[0097] Step 2: Under an inert gas environment, cool the reaction system to 0℃~30℃ and stir the reaction for 12h~48h;

[0098] Step 3: Distill the liquid in the reaction system under reduced pressure to obtain a viscous solid. Wash the solid with a certain amount of hexane solvent, filter it under pressure multiple times, and dry it to obtain a powdered solid catalyst.

[0099] This invention does not specifically limit the inert gas, such as nitrogen, argon, etc.

[0100] In another specific embodiment, the preparation method of the non-metallocene catalyst of the present invention includes the following steps:

[0101] Step 1: Dissolve 0.2-2 mmol of aryl ligand in a certain amount of organic solvent and stir until dissolved to obtain component A solution;

[0102] (2) Dissolve 0.2-1.5 mmol of a transition metal compound in a certain amount of organic solvent and stir thoroughly to obtain component B solution;

[0103] (3) While stirring, slowly add component B solution to component A solution at a temperature of 0℃~50℃, and reflux at a constant temperature of 50℃~120℃ for 1h~4h;

[0104] (4) Under an inert gas environment, the reaction system is cooled to 0℃~30℃ and stirred for 12h~48h.

[0105] (5) The liquid in the reaction system was distilled under reduced pressure to obtain a viscous solid. A certain amount of hexane solvent was used to wash and filter the solid three times. The solid was then dried to obtain a powdered solid catalyst.

[0106] The present invention also provides the application of the above-mentioned non-metallocene catalyst in olefin polymerization, that is, using the above-mentioned non-metallocene catalyst as the main catalyst and organoaluminum as the co-catalyst to catalyze the homopolymerization or copolymerization reaction of olefins.

[0107] In one embodiment, the above-mentioned olefin polymerization is carried out using a solution polymerization process, with the above-mentioned non-metallocene catalyst as the main catalyst and organoaluminum as the co-catalyst, for homopolymerization of ethylene or polymerization of ethylene with C3-C4 polymers. 12 Olefin polymers were obtained by copolymerizing α-olefins.

[0108] In one embodiment, the organoaluminum cocatalyst of the present invention is MAO (methylaluminoxane). To reduce production costs, the organoaluminum cocatalyst can be an alkylaluminum, the general formula of which can be represented by the following chemical formula: AlR3. Wherein, the groups R can be the same or different, and are selected from C1 to C8 alkyl groups. Specifically, they can be selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisohexylaluminum, diethylmethylaluminum, dimethylethylaluminum, or other alkylaluminums, with trimethylaluminum, triethylaluminum, and triisobutylaluminum being preferred, further preferred being trimethylaluminum and triethylaluminum, and most preferably triethylaluminum.

[0109] In another embodiment, the organoaluminum cocatalyst of the present invention is a haloalkylaluminum, which can be represented by the following chemical formula: AlR n X (3-n) In this embodiment, the groups R can be the same or different, and each group is selected from C1 to C8 alkyl groups; the group X is a halogen, preferably chlorine; and n is 1 to 2. Specifically, the aluminum alloy can be selected from dimethylaluminum chloride, dichloromethylaluminum chloride, diethylaluminum chloride, dichloroethylaluminum chloride, dipropylaluminum chloride, dichloropropylaluminum chloride, di-n-butylaluminum chloride, di-n-butylaluminum chloride, dichloropropylaluminum chloride, di-n-butylaluminum chloride, di-n-pentylaluminum chloride, di-n-pentylaluminum chloride, di-isopentylaluminum chloride, di-isopentylaluminum chloride, di-n-hexylaluminum chloride, di-n-hexylaluminum chloride, di-isohexylaluminum chloride, dichloromethylethylaluminum chloride, dichloromethylpropylaluminum chloride, dichloromethyl-n-butylaluminum chloride, dichloromethylisobutylaluminum chloride, dichloroethylpropylaluminum chloride, dichloroethyl-n-butylaluminum chloride, dichloromethylisobutylaluminum chloride, sesquihexylaluminum chloride, or other chloroalkylaluminum, with diethylaluminum chloride and sesquihexylaluminum chloride being preferred, and sesquihexylaluminum chloride being the most preferred.

[0110] In one embodiment, the solvent for olefin polymerization can be selected from C4 to C6. 10 Alkanes, halogenated C1-C 10 Alkanes, C6-C 10 Cycloalkanes or C6-C 20Aromatic hydrocarbons; specifically, they may be selected from butane, pentane, hexane, heptane, octane, nonane, decane, dichloromethane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, xylene or other organic solvents, with n-hexane, n-heptane and toluene being preferred, and toluene being the most preferred.

[0111] The technical solution of the present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following embodiments.

[0112] Example 1

[0113] Under a nitrogen atmosphere, 124 mg of 2-methoxyphenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, resulting in an anhydrous transparent solution A. Under a nitrogen atmosphere, 104 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, resulting in an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 60 °C and refluxed with stirring for 3 h. The mixture was then cooled to room temperature and stirred for 24 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0114] This non-metallocene catalyst is designated CAT-1.

[0115] Example 2

[0116] Under a nitrogen atmosphere, 124.1 mg of 4-methoxyphenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 102 mg of zirconium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 80 °C and refluxed with stirring for 2 h. The temperature was then lowered to 30 °C and the mixture was stirred for 12 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0117] This non-metallocene catalyst is designated CAT-2.

[0118] Example 3

[0119] Under a nitrogen atmosphere, 138.1 mg of 2-methoxy-4-methylphenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 99 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at a temperature of 50 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 80 °C and refluxed with stirring for 2 h. The temperature was then lowered to 0 °C and the mixture was stirred for 48 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0120] This non-metallocene catalyst is designated CAT-3.

[0121] Nuclear magnetic resonance (NMR) measurements were performed on CAT-3 for structural analysis, and the resulting carbon NMR spectrum is shown below. Figure 1 As shown in the figure, the carbon NMR spectrum shows nine peaks, corresponding to nine carbon atoms in different chemical environments. Further analysis reveals the chemical structure of CAT-3 as follows.

[0122]

[0123] Example 4

[0124] Under a nitrogen atmosphere, 165.2 mg of 2-tert-butyl-4-methylphenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 162 mg of hafnium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of n-hexane. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 120 °C and refluxed with stirring for 1 h. The mixture was then cooled to room temperature and stirred for 24 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0125] This non-metallocene catalyst is designated CAT-4.

[0126] Example 5

[0127] Under a nitrogen atmosphere, 152.1 mg of 2-propoxyphenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 95.8 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of xylene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 60 °C and refluxed for 3 h. The mixture was then cooled to room temperature and stirred for 16 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0128] This non-metallocene catalyst is designated CAT-5.

[0129] Nuclear magnetic resonance (NMR) measurements were performed on CAT-5 for structural analysis. The resulting carbon NMR spectrum is shown below. Figure 2 As shown. The carbon NMR spectrum shows seven peaks, corresponding to seven carbon atoms in seven different chemical environments. Further analysis reveals the chemical structure of CAT-5:

[0130]

[0131] Example 6

[0132] Under a nitrogen atmosphere, 207.5 mg of 2-bromo-4-chlorophenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 97.2 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 60 °C and refluxed with stirring for 3 h. The mixture was then cooled to room temperature and stirred for 24 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0133] This non-metallocene catalyst is designated CAT-6.

[0134] Example 7

[0135] Under a nitrogen atmosphere, 157.1 mg of 3-fluoro-4-nitrophenol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 105 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 60 °C and refluxed for 3 h. The mixture was then cooled to room temperature and stirred for 24 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0136] This non-metallocene catalyst is designated CAT-7.

[0137] Example 8

[0138] Under a nitrogen atmosphere, 174.2 mg of 6-methoxynaphthol was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 96.3 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 100 °C, and the mixture was stirred and refluxed for 3 h. The temperature was then lowered to room temperature, and the mixture was stirred for 36 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0139] This non-metallocene catalyst is designated CAT-8.

[0140] Example 9

[0141] Under a nitrogen atmosphere, 356.1 mg of 2,2'-thio(4,6-dichlorophenol) was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, yielding an anhydrous transparent solution A. Under a nitrogen atmosphere, 104 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, yielding an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 80 °C and refluxed with stirring for 3 h. The mixture was then cooled to room temperature and stirred for 18 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0142] This non-metallocene catalyst is designated CAT-9.

[0143] Example 10

[0144] Under a nitrogen atmosphere, 123.2 mg of 4-methoxyaniline was weighed and added to a 100 ml Schlenk flask, followed by 30 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution A. Under a nitrogen atmosphere, 97.2 mg of titanium tetrachloride was added to a 50 ml round-bottom flask, followed by 20 ml of toluene. The mixture was stirred for 5–10 min until completely miscible, forming an anhydrous transparent solution B. Under stirring, at 0 °C, solution B was slowly added dropwise to solution A. After the addition was complete, the mixture was stirred for 10 min until completely miscible. The temperature was then raised to 100 °C, and the mixture was stirred and refluxed for 3 h. The temperature was then lowered to room temperature, and the mixture was stirred for 24 h. The solvent was removed by vacuum distillation, and the product was separated. The product was washed three times with n-hexane and dried to obtain an orange-yellow solid powder catalyst.

[0145] This non-metallocene catalyst is designated CAT-10.

[0146] Examples 11-20

[0147] Examples 11-20 illustrate the application of catalyst CAT1-10 in olefin polymerization.

[0148] The polymerization experiment process is as follows:

[0149] In a 250 ml stainless steel high-pressure polymerization reactor, the mixture was purged three times each with nitrogen and ethylene, and the temperature was raised to 100 °C. Then, 50 ml of toluene solvent and 10 ml of MAO (10% toluene solution) co-catalyst were added via a feeder. 2.0 mg of the main catalyst (the non-metallocene catalyst from Examples 1-10) was weighed out and rinsed with 50 ml of toluene solvent. The reaction solution in the feed hopper was then added to the high-pressure polymer reactor, and the pressure was raised to and maintained at 2.0 MPa. The reaction was carried out at 80 °C for 0.5 hours. After the polymerization reaction was completed, the reactor was cooled and degassed. Then, acidic methanol (5%, v / v) was slowly poured in to precipitate the polymer. The produced polymer powder was filtered, washed, and finally dried at 80 °C. Specific polymerization results are listed in Table 1.

[0150] Table 1 Results of catalytic ethylene polymerization

[0151]

[0152] Comparative Examples

[0153] The polymerization conditions in the comparative example were the same as those in Examples 1-10, except that the catalyst used was 2-(hydroxy, diphenyl-methyl)phenol titanium, denoted as catalyst CAT-11. The polymerization results are shown in Table 2.

[0154] Table 2. Ethylene polymerization results using catalysts 8 and 11.

[0155]

[0156] As shown in Table 2, the molecular weight of polyethylene obtained by CAT-11 catalytic polymerization exceeds 1 million, making it unsuitable for preparing low molecular weight polyethylene. Therefore, this catalyst cannot be used to prepare polyethylene wax.

[0157] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a non-metallocene catalyst, characterized in that, Includes the following steps: Step 1: Mix the transition metal compound with the aryl ligand and react at 50℃~120℃; Step 2: Cool the mixture obtained in Step 1 to 0℃~30℃ and continue the reaction in an inert gas environment for 12h~48h; Step 3: The mixture obtained in Step 2 is post-processed and dried to obtain a non-metallocene catalyst; Wherein, the transition metal compound is a compound of a Group IVB transition metal, and the aryl ligand is an arylphenol, aryl sulfide, or arylamine with or without substituents.

2. The method for preparing the non-metallocene catalyst according to claim 1, characterized in that, The transition metal compound is a compound of Ti, Zr, or Hf, and the substituent is selected from hydrogen, substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbons, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbons, oxygen-containing groups, sulfur-containing groups, or halogen atoms.

3. The method for preparing the non-metallocene catalyst according to claim 2, characterized in that, The transition metal compound is a chloride of Ti, Zr, or Hf, and the substituent is selected from aliphatic hydrocarbon groups having 1 to 12 carbons, aromatic hydrocarbon groups having 6 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkylthio groups having 1 to 12 carbons, or halogen atoms.

4. The method for preparing the non-metallocene catalyst according to claim 1, characterized in that, The aryl ligand contains at least two substituents located on adjacent carbons of the aryl ligand, and the at least two substituents form a cyclic structure, which are substituted or unsubstituted C4-C8 conjugated olefin groups.

5. The method for preparing the non-metallocene catalyst according to claim 4, characterized in that, The at least two substituents form a cyclic structure and are either unsubstituted C4-C8 conjugated olefin groups or C4-C8 conjugated olefins containing alkoxy substituents, alkylthio substituents or halogen substituents.

6. The method for preparing the non-metallocene catalyst according to claim 1, characterized in that, The transition metal compound and the aryl ligand are dissolved separately in an organic solvent and then mixed. The organic solvent is selected from C4 to C5. 10 Alkanes, halogenated C1-C 10 Alkanes, C6-C 10 Cycloalkanes or C6-C 20 Aromatic hydrocarbons.

7. A method for ethylene polymerization, characterized in that, The non-metallocene catalyst obtained by the preparation method according to any one of claims 1-6 is the main catalyst.

8. The olefin polymerization method according to claim 7, characterized in that, This olefin polymerization method uses organoaluminum as a co-catalyst.

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