Internal electron donor compound, catalyst component and olefin polymerization method

Abstract

The invention discloses an internal electron donor compound, a catalyst component and an olefin polymerization method, and the internal electron donor compound has a structure as shown in a formula I. When a catalyst prepared from the internal electron donor is used for olefin polymerization, the catalyst has excellent activity and lower xylene soluble substances.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of olefin polymerization catalysts, and relates to an internal electron donor compound for olefin polymerization, such as alpha-olefin polymerization, a catalyst component and an olefin polymerization method. BACKGROUND

[0002] It is well known that the Ziegler-Natta catalysts for olefin polymerization comprise three parts of a magnesium chloride carrier, an internal electron donor compound and a titanium compound, wherein the internal electron donor compound can not only improve the activity of the catalyst, but also enhance the stereospecificity of the catalyst. If the catalyst lacks a suitable internal electron donor compound, the activity of the catalyst will be affected, and the polymer prepared therefrom may have low isotacticity, leading to production difficulties and limiting end applications.

[0003] Up to now, a series of compounds have been widely used as internal electron donors to prepare Ziegler-Natta catalysts, such as aromatic monoester or diester compounds, such as diisobutyl phthalate or ethyl benzoate, used in US4784983A, diol ester compounds used in CN1453298A, succinic acid ester compounds used in CN1313869A, diether compounds used in EP0361494A, salicylic acid ester compounds used in CN1257920C / CN104829757B, 1,2-phenylene aromatic diester compounds used in US61141902A, amide or amide ester compounds used in EP15186252A / CN108570120A, etc. However, in industrial production, each of these internal electron donor compounds has certain defects in practical application, such as: the catalyst using aromatic diester compounds has low catalytic activity; the catalyst using diether compounds has high catalytic activity and good hydrogen regulation sensitivity, but the obtained polymer has poor regioselectivity; the catalyst using salicylic acid ester compounds has general activity and high xylene solubles; the catalyst using 1,2-phenylene aromatic diester compounds has good catalytic activity and hydrogen regulation sensitivity, but the obtained polymer has relatively high xylene solubles; the catalyst using amide or amide ester compounds has low activity and high xylene solubles.

[0004] Because of the importance of the role played by the internal electron donor compound in the catalyst and the existing defects of the current internal electron donor compounds in practical application, the improvement of the internal electron donor compound has always been a research hotspot in the field.

[0005] Phthalate compounds as plasticizer substances, its potential harm to human health is more and more attention, which also limits its use in Ziegler-Natta catalyst; second, different internal electron donor on the performance of Ziegler-Natta catalyst is important, by developing different internal electron donor to obtain different functions of high efficiency catalyst, which is important for the further development of polyolefin industry.

[0006] Therefore, it is of great significance to develop a new internal electron donor which can overcome the defects of the prior art for preparing olefin polymerization catalyst. SUMMARY

[0007] The purpose of the present application is to provide an internal electron donor compound, catalyst component and olefin polymerization method to improve the catalytic activity of the catalyst in olefin polymerization.

[0008] To achieve the above-mentioned purpose of one aspect, the internal electron donor compound of the present application adopts the following technical scheme:

[0009] An internal electron donor compound for a catalyst for olefin polymerization, the internal electron donor compound has the following formula I structure:

[0010]

[0011] In formula I,

[0012] G contains 4-30, such as 6, 8, 10, 15, 18, 20, 25, 5-25, 7-20 or 9-14, and is a substituted or unsubstituted alkyl group containing at least two rings, such as cycloalkyl, heteroatom-containing substituted heteroaryl containing at least two rings, amino containing at least two rings, such as two H on the amino group are replaced by one ring, for example, replaced by a five-membered ring or a six-membered ring, wherein, it is understood in the art that the two rings between the amino group can also be connected by a carbon-carbon bond, thereby further forming a nitrogen heterocycle;

[0013] R1-R3 are the same or different, each independently selected from H, halogen, C2-C18 alkenyl, C1-C18 substituted or unsubstituted straight-chain alkyl or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, and two or more of R1-R3 can be bonded to each other to form a ring or an unsaturated bond;

[0014] A, B are the same or different, each independently selected from ester group, amino group, amide group, sulfonyl ester group and sulfonamide group;

[0015] Wherein, the substituent group for substitution is a rare group, halogen or heteroatom; the heteroatom is selected from N, O, S, P, Si.

[0016] In some embodiments, in formula I, A and B, the ester group is selected from R4COO-, R5OOC-, and R6R7NCOO-; the amino group is selected from R6R7N-; the amide group is selected from R8CONR9- and R 10 R 11 NCO-; the sulfonyl ester group is selected from R 12 SO3-; the sulfonamide group is selected from R 11 SO2R 13 N-; wherein R4-R 13 are the same or different, each independently selected from H, halogen, C2-C18 alkenyl, C1-C18 substituted or unsubstituted linear or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; wherein the substituents for substitution are alkyl, halogen or heteroatoms; the heteroatoms are selected from N, O, S, P, Si.

[0017] In formula I of the present application, G has a carbon number of 4-30, such as 6, 8, 10, 20 or 25, which contains two, three, four or more five-membered and / or six-membered rings, such as cycloalkyl or aryl; in some embodiments, the carbons in the meta- or para- position of a single ring can be connected by linear or branched alkyl to form multiple rings; in preferred embodiments, the structure of G in formula I is adamantyl, norbornyl, N,N-dicyclopentylamino or carbazolyl. It has been found that after such modification of the G position with a multi-ring compound, the prepared catalyst shows higher catalytic activity and hydrogen sensitivity in propylene polymerization, and the prepared polymer has relatively lower xylene solubles and wider molecular weight distribution.

[0018] In preferred embodiments, the internal electron donor compound is selected from the following compounds:

[0019]

[0020]

[0021] To achieve the above-mentioned object of the present application, in another aspect, the catalyst component of the present application uses the following technical solution:

[0022] A catalyst component for olefin polymerization, characterized in that the catalyst component comprises a titanium compound, a magnesium compound and an internal electron donor compound as described above.

[0023] In the art, the titanium compound and the magnesium compound used in combination with the internal electron donor are well known in the art. In some embodiments, the precursor of the magnesium compound is selected from at least one of: X n Mg(OR) 2-nMgCl2.mROH, MgCl2 / SiO2, MgCl2 / Al2O3, or a mixture of magnesium halide and titanium alcoholate, wherein m is 1-6, 0n<2, X is halogen, and R is hydrogen or a C1-C8 hydrocarbon group; preferably, the magnesium compound is magnesium halide or diethoxy magnesium.

[0024] In the present application, the magnesium halide precursor can be X n Mg(OEt) 2-n MgCl2.mEtOH, wherein m is 1-6, 0n<2, and X is halogen.

[0025] In some embodiments, the general formula of the titanium compound is TiX n (OR) 4-n wherein R is a hydrocarbon group having 1-20 carbon atoms, X is halogen, and n = 1-4. Preferably, the titanium compound is titanium tetrachloride.

[0026] In some embodiments, the catalyst component is prepared by contacting the magnesium compound, the titanium compound, and the internal electron donor compound to obtain the catalyst component, which is well known in the art; the ratio of the internal electron donor compound, the magnesium compound precursor, and the titanium compound can be 1:(5-50):(20-500), for example, when the amount of the internal electron donor compound is 1 part by weight, the amount of the magnesium compound precursor can be 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by weight, and the amount of the titanium compound can be 20, 40, 60, 100, 200, 300, 400, or 500 parts by weight.

[0027] In preferred embodiments, the catalyst component is prepared by the following process:

[0028] In a reactor with filtration function with stirring, 2-2.5 parts by weight of diethoxy magnesium and 50-60 parts by weight of chlorobenzene are added, then 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added dropwise at room temperature, then heated to 85-95℃ such as 88, 90 or 92℃, 1-2 parts by weight such as 1.2, 1.5 or 1.8 parts by weight of the internal electron donor compound is added, and then heated to 100-120℃ such as 105, 110 or 115℃ for 0.5-2 hours such as 1 or 1.5 hours, then solid-liquid separation is carried out, then 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added again, and then heated to 100-120℃ such as 105, 110 or 115℃ for 0.5-2 hours such as 1 or 1.5 hours, then solid-liquid separation is carried out again, then 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added again and heated to 100-120℃ such as 105, 110 or 115℃ for 15-45 minutes such as 20, 30, 35 or 40 minutes, then solid-liquid separation is carried out, then washed with n-heptane and dried to obtain the catalyst component; wherein the volume ratio of titanium tetrachloride to chlorobenzene in the titanium tetrachloride / chlorobenzene solution is (4:6)-(6:4) such as 5:4, 5:5 or 4:5.

[0029] In another aspect to achieve the above-mentioned object, the olefin polymerization method of the present application uses the following technical solution:

[0030] An olefin polymerization method, the method is to polymerize olefin monomers in the presence of a catalyst obtained by reacting an organoaluminum compound, a siloxane compound and the above-mentioned catalyst component to form a polymer; preferably, the olefin is propylene.

[0031] In some embodiments, the method comprises:

[0032] Step one, the reactor is replaced with nitrogen, then liquid propylene and hydrogen are sequentially added at room temperature, and heated to a set temperature;

[0033] Step two, the heptane solution of the organoaluminum compound, the hexane solution of the siloxane compound as the external electron donor and the above-mentioned catalyst component are mixed and reacted to form a catalyst, and then the mixture is injected into the reactor to start the reaction when the reactor reaches the set temperature to obtain a polymer;

[0034] The set temperature is 65-75℃ such as 68, 70 or 72℃.

[0035] In some embodiments, the ratio of the catalyst component, the organoaluminum compound, and the siloxane compound is 1 : (5-200) : (5-50), for example, the amount of the organoaluminum compound can be 5, 10, 20, 50, 100, 150, or 200 parts by weight, and the amount of the siloxane compound can be 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by weight, based on 1 part by weight of the catalyst component.

[0036] In some embodiments, the organoaluminum compound has the general formula AlR n X (3-n) In some embodiments, the organoaluminum compound has the general formula AlR

[0037] In some embodiments, the siloxane compound has the general formula R n Si(OR1) 4-n wherein R and R1 are C1-C18 hydrocarbon groups, optionally with heteroatoms; n is an integer from 0 ≦ n ≦ 3, such as 1 or 2; the siloxane compound of the external electron donor is dicyclopentyl dimethoxysilane, cyclohexyl methyl dimethoxysilane, or dimethoxy diphenyl silane; preferably, the siloxane compound is dicyclopentyl dimethoxysilane.

[0038] Compared with the prior art, the present application has the following advantages:

[0039] The catalyst prepared using the internal electron donor of the present application has high activity and good hydrogen sensitivity, and when used for the polymerization of olefins such as propylene, has excellent activity and low xylene solubles; and under the same preparation process, the catalyst prepared using the adamantane, norbornane-modified internal electron donor has more sensitive hydrogen sensitivity and lower hydrogen effect on xylene solubles. DETAILED DESCRIPTION

[0040] In order to facilitate the understanding of the present application, the present application will be further described below in conjunction with examples. It should be understood that the following examples are only for better understanding of the present application, and do not mean that the present application is limited to the following examples only.

[0041] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The term "and / or" as used herein may include any and all combinations of one or more of the associated listed items. The terms "first," "second," "third," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0043] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in this technical field can be followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0044] The polymer-related data in the examples were obtained using the following test methods:

[0045] 1. Melt Flow Rate (MFR): Tested according to ASTM D1238;

[0046] 2. Xylene soluble matter (XS): Detected using a fully automated xylene soluble matter analyzer (CRYSTEX QC) from Polymer Char.

[0047] 3. Molecular weight and its distribution: Detection was performed using a PolymerCharts high-temperature gel permeation chromatography system (GPC-IR6).

[0048] 4. Activity: The weight of product obtained by catalytic polymerization per gram of catalyst per hour.

[0049] The internal electron donors used in the following examples / comparative examples are described below:

[0050] (ID1) Chemical name: 3-methyl-5-adamantyl-1,2-dibenzoyloxybenzene

[0051] The preparation method is as follows:

[0052] In a 500 mL flask, 25.8 g (100 mmol) of 3-methyl-5-adamantyl-1,2-o-diphenol and approximately 30 g (3 eq) of triethylamine were added, along with approximately 300 mL of dichloromethane (DCM). The mixture was stirred at room temperature, and 32 g (2.2 eq) of benzoyl chloride was slowly added dropwise to the flask. The mixture was stirred at room temperature for approximately 5 h until the reaction was complete. The reactants were transferred to a 1000 mL flask, and the DCM was removed by rotary evaporation at room temperature. After removal, 150 mL of diethyl ether and 200 mL of water were added to the flask, and the mixture was extracted using a separatory funnel. The organic phase was separated and washed twice with 200 mL of water. The solution was then dried over anhydrous sodium sulfate, filtered, and the organic phase was obtained. Rotary evaporation of the organic phase yielded a pale yellow solid. Recrystallization from ethyl acetate / petroleum ether (1:20) yielded a white solid product in 89% yield.

[0053] 1 ¹H NMR and LC-MS (m / z) (M+) data are as follows: ¹H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.00-7.98 (4H), 7.48-7.45 (2H), 7.36-7.24 (4H), 7.22 (1H), 7.15 (1H), 2.18 (3H), 2.02-1.97 (9H), 1.70 (6H); LC-MS (m / z) (M+): 466.29.

[0054] (ID2) Chemical name: 3-methyl-5-adamantyl-2-benzoyloxybenzoate n-butyl ester

[0055] The preparation method is as follows:

[0056] 28.6 g (100 mmol) of 3-methyl-5-adamantyl-2-hydroxybenzoic acid, about 300 mL of DCM, and 20 mL of THF (tetrahydrofuran) were added to a 500 mL flask. The mixture was stirred at room temperature, and 25 g (1.2 eq) of DCC (dicyclohexylcarbodiimide) was slowly added. After the addition was complete, the mixture was stirred at room temperature for 2 h. Then, 15 g of n-butanol was slowly added dropwise to the reaction system. The mixture was stirred at room temperature for another 5 h. The mixture was filtered, and the organic phase was concentrated to obtain n-butyl 3-methyl-5-adamantyl-2-hydroxybenzoic acid.

[0057] The obtained product was dissolved in about 300 mL of DCM, and 30 g (3 eq) of triethylamine was added. Under ice-water bath conditions, 17 g (1.2 eq) of benzoyl chloride was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 h, filtered, and the organic phase was concentrated. The target compound was then recrystallized from ethyl acetate / petroleum ether (1:50) with a yield of 78%.

[0058] 1¹H NMR and LC-MS (m / z) (M+) data are as follows: ¹H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.24-7.22 (2H), 7.88-7.87 (¹H), 7.65-7.61 (2H), 7.53-7.43 (2H), 3.93-3.91 (2H), 2.27 (3H), 2.14-2.09 (4H), 1.87 (6H), 1.80-1.73 (6H), 1.41-1.37 (2H), 1.27-1.21 (2H), 0.77-0.74 (3H); LC-MS (m / z) (M+): 446.35.

[0059] (ID3) Chemical name: Isobutyl 3-methyl-5-adamantyl-2-benzoyloxybenzoate

[0060] The preparation method for ID3 is the same as that for ID2, except that n-butanol is replaced with isobutanol.

[0061] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.24-8.22 (2H), 7.88-7.87 (1H), 7.65-7.61 (2H), 7.53-7.43 (2H), 3.93-3.91 (2H), 2.25 (3H), 2.12 (3H), 1.93 (6H), 1.83-1.72 (7H), 0.83-0.81 (6H); LC-MS (m / z) (M+): 446.35.

[0062] (ID4) Chemical name: 2,3-dihydro-4-benzoyloxy-7-adamantyl-1H-indene-5-carboxylic acid n-butyl ester

[0063] The preparation method for ID4 is the same as that for ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 2,3-dihydro-4-hydroxy-7-adamantyl-1H-indene-5-carboxylic acid.

[0064] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.22-8.20 (2H), 7.86 (1H), 7.62-7.61 (1H), 7.52-7.48 (2H), 3.93-3.91 (2H), 3.07 (2H), 2.59 (2H), 2.15-2.10 (5H), 2.02 (6H), 1.79-1.73 (6H), 1.41-1.37 (2H), 1.27-1.21 (2H), 0.77-0.74 (3H); LC-MS (m / z) (M+): 472.39.

[0065] (ID5) Chemical name: Isobutyl 4-adamantyl-5,6,7,8-tetrahydro-1-benzoyloxy-2-naphthoic acid

[0066] The preparation method for ID5 is the same as that for ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 4-adamantyl-5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid, and n-butanol is replaced with isobutanol.

[0067] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.26-8.24 (2H), 7.81-7.79 (1H), 7.68-7.64 (1H), 7.56-7.52 (2H), 4.12-4.09 (2H), 2.96-2.76 (4H), 2.33-2.00 (4H), 1.73-1.70 (1H), 0.83-0.81 (15H); LC-MS (m / z) (M+): 486.45.

[0068] (ID6) Chemical name: 4-adamantyl-1-benzoyloxy-2-naphthoic acid n-butyl ester

[0069] The preparation method for ID6 is the same as that for ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 4-adamantyl-1-hydroxy-2-naphthoic acid.

[0070] 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.41-8.39 (2H), 8.09-8.06 (1H), 7.91-7.82 (2H), 7.78-7.62 (3H), 7.59-7.54 (2H), 4.15 -4.12(2H),2.12(3H),1.92(6H),1.77-1.72(6H),1.41-1.37(2H),1.27-1.21(2H),0.77-0.74(3H); LC-MS(m / z)(M+): 482.29.

[0071] (ID7) Chemical name: Isobutyl 3-methyl-5-norborneol-2-benzoyloxybenzoate

[0072] The preparation method for ID7 is the same as that for ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 3-methyl-5-borneol-2-benzoyloxybenzoic acid, and n-butanol is replaced with isobutanol.

[0073] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.24-8.22 (2H), 7.88-7.87 (1H), 7.65-7.61 (2H), 7.53-7.43 (2H), 3.93-3.91 (2H), 2.95-2.91 (1H), 2.56-2.49 (2H), 2.25 (3H), 1.89-1.84 (1H), 1.74-1.66 (5H), 1.50-1.36 (3H), 0.83-0.81 (6H); LC-MS (m / z) (M+): 406.29.

[0074] (ID8) Chemical name: Isobutyl 3-methyl-5-(dicyclopentaneamino)-2-benzoyloxybenzoate

[0075] The preparation method for ID8 is the same as that for ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 3-methyl-5-(dicyclopentaneamino)-2-hydroxybenzoic acid, and n-butanol is replaced with isobutanol.

[0076] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.22-8.20 (2H), 7.89-7.87 (1H), 7.67-7.61 (2H), 7.53-7.41 (2H), 3.93-3.91 (2H), 2.25 (3H), 3.10-3.08 (2H), 1.93-1.81 (4H), 1.74-1.61 (4H), 1.58-1.46 (4H), 1.35-1.21 (4H), 0.83-0.81 (6H); LC-MS (m / z) (M+): 463.33.

[0077] (ID9) Chemical name: Isobutyl 3-methyl-5-(9-carbazolyl)-2-benzoyloxybenzoate

[0078] The preparation method of ID9 is the same as that of ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 3-methyl-5-(9-carbazolyl)-2-hydroxybenzoic acid, and n-butanol is replaced with isobutanol.

[0079] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.24-8.22 (2H), 8.14-8.12 (2H), 7.88-7.87 (1H), 7.65-7.43 (5H), 7.45-7.38 (3H), 7.30-7.23 (2), 3.93-3.91 (2H), 2.25 (3H), 1.73-1.71 (1H), 0.83-0.81 (6H); LC-MS (m / z) (M+): 477.35.

[0080] (ID10) Chemical name: Isobutyl 4-norborneol-1-benzoyloxy-2-benzoate

[0081] The preparation method for ID10 is the same as that for ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid is replaced with 4-norbornyl-1-amino-2-benzoic acid, and n-butanol is replaced with isobutanol.

[0082] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.24-8.22 (2H), 7.89-7.88 (1H), 7.87-7.79 (3H), 7.53-7.43 (2H), 3.93-3.91 (2H), 2.95-2.91 (1H), 2.56-2.49 (2H), 1.89-1.84 (1H), 1.74-1.66 (5H), 1.50-1.36 (3H), 0.83-0.81 (6H); LC-MS (m / z) (M+): 391.43.

[0083] (ID11) Chemical name: 2,3-dihydro-7-adamantyl-4,5-dibenzoyloxy-1H-indene

[0084] The preparation method of ID11 is the same as that of ID1, except that 3-methyl-5-adamantyl-1,2-catechol is replaced with 2,3-dihydro-7-adamantyl-4,5-hydroxy-1H-indene.

[0085] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.00-7.98 (4H), 7.45-7.42 (2H), 7.32-7.27 (4H), 7.02 (1H), 3.18-3.14 (2H), 2.74-2.71 (2H), 2.03-1.97 (11H), 1.70 (6H); LC-MS (m / z) (M+): 492.35.

[0086] (ID12) Chemical name: 3-methyl-5-adamantyl-1,2-dimethylsulfonyloxybenzene

[0087] The preparation method for ID12 is the same as that for ID1, except that benzoyl chloride is replaced with methanesulfonyl chloride.

[0088] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 7.36 (1H), 7.28 (1H), 3.55 (3H), 3.49 (3H), 2.36 (3H), 2.08 (3H), 1.86 (6H), 1.74 (6H); LC-MS (m / z) (M+): 414.21.

[0089] (ID13) Chemical name: 3-methyl-5-adamantyl-1,2-dibenzenesulfonyloxybenzene

[0090] The preparation method for ID13 is the same as that for ID1, except that benzoyl chloride is replaced with benzenesulfonyl chloride.

[0091] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 7.87.00-7.78 (4H), 7.71-7.65 (2H), 7.63-7.57 (4H), 7.24 (1H), 6.75 (1H), 2.12 (3H), 2.05 (3H), 1.72-1.65 (12H); LC-MS (m / z) (M+): 538.25.

[0092] (ID14) Chemical name: 3-methyl-5-adamantyl-1,2-dibenzenesulfonyloxybenzene

[0093] The preparation method of ID14 is the same as that of ID1, except that benzoyl chloride is replaced with N,N-diethylaminocarbonyl chloride.

[0094] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 7.10 (1H), 6.95 (1H), 3.35-3.24 (8H), 2.12 (3H), 2.05 (3H), 1.84 (6H), 1.72 (6H), 1.17-1.06 (12H); LC-MS (m / z) (M+): 458.49.

[0095] (C1)DNBP, chemical name: di-n-butyl phthalate; from JP62158704 A;

[0096] (C2) Chemical name: 3-methyl-5-tert-butyl-1,2-dibenzoyloxybenzene, from WO2010078485A1;

[0097] (C3) Chemical name: 3-methyl-5-tert-butyl-2-benzoyloxybenzoate (n-butyl ester);

[0098] The preparation method for C3 is the same as that for ID15 below, except that 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid is replaced with 3-methyl-5-tert-butyl-2-hydroxybenzoic acid;

[0099] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.23-8.21 (2H), 7.86-7.77 (2H), 7.64-7.62 (1H), 7.55-7.49 (2H), 4.01-3.90 (2H), 2.10 (3H), 1.42-1.37 (2H), 1.26-1.21 (2H), 0.81-0.76 (12H); LC-MS (m / z) (M+): 368.51.

[0100] (C4) Chemical name: Isobutyl 2,3-dihydro-4-benzoyloxy-7-tert-butyl-1H-indene-5-carboxylate;

[0101] The preparation method is as follows:

[0102] In a 500 mL flask, 100 mmol of 2,3-dihydro-4-hydroxy-7-tert-butyl-1H-indene-5-carboxylic acid, approximately 300 mL of DCM (dichloromethane), and 20 mL of THF (tetrahydrofuran) were added. The mixture was stirred at room temperature, and 25 g (1.2 eq) of DCC (dicyclohexylcarbodiimide) was slowly added. After the addition was complete, the mixture was stirred at room temperature for 2 h. Then, 15 g of n-butanol was slowly added dropwise to the reaction system, and the mixture was stirred at room temperature for another 5 h. The mixture was filtered, and the organic phase was concentrated. The concentrated product was then dissolved in approximately 300 mL of DCM, and 30 g (3 eq) of triethylamine was added. Under ice-water bath conditions, 17 g (1.2 eq) of benzoyl chloride was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 h, filtered, and the organic phase was concentrated. The target compound was obtained by recrystallization from ethyl acetate / petroleum ether (1:50).

[0103] The 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400MHz, CDCl3, 25℃, TMS): δ (ppm) 8.23-8.21 (2H), 7.86 (1H), 7.63-7.61 (1H), 7.52-7.48 (2H), 3.93-3.92 (2H), 2.90-2.87 (4H), 2.15-2.10 (2H), 1.73-1.70 (1H), 0.83-0.81 (15H); LC-MS (m / z) (M+): 394.27.

[0104] Catalyst component preparation example 1

[0105] In a 250 mL reactor equipped with a stirrer and filter, fully purged with nitrogen, 2.2 g of magnesium diethoxy and 50 mL of chlorobenzene were added. Then, 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio 1:1) was added dropwise while maintaining room temperature. The temperature was then slowly raised to 90 °C, and 1.5 g of ID1 was added. The temperature was then raised to 110 °C and held for 1 hour. The liquid was then filtered clean, and the residue was discarded. Another 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio 1:1) was added, and the reaction was held at 110 °C for 1 hour. The liquid was then filtered clean, and another 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio 1:1) was added, and the reaction was held at 110 °C for 0.5 hours. The liquid was then filtered clean, and the solid was washed with 100 mL of n-heptane three times. The residue was then filtered off and dried to obtain a solid powder, which is the prepared catalyst component 1#. The titanium content, internal electron donor content, and polymerization data of catalyst component 1 are shown in Table 1 below.

[0106] Catalyst component preparation examples 2-14

[0107] The difference from Example 1 of catalyst component preparation is that the internal electron donor ID1 is replaced with ID2-ID14, and the addition of titanium tetrachloride is adjusted accordingly. The titanium content, internal electron donor content, and polymerization data of the prepared catalyst components 2#-14# are shown in Table 1 below.

[0108] Catalyst component preparation comparative examples 1-4

[0109] The difference from Example 1 of catalyst component preparation is that the internal electron donor ID1 is replaced with C1-C4, and the addition of titanium tetrachloride is adjusted accordingly. The titanium content, internal electron donor content, and polymerization data of the prepared catalyst components C1#-C4# are shown in Table 1 below.

[0110] Polymerization Example a1:

[0111] Propylene polymerization was carried out in a 5L stainless steel polymerization reactor in the laboratory.

[0112] Step 1: First, purge the reactor with purified nitrogen (water content <1ppm, oxygen content <1ppm); then, sequentially add 2.2L of liquid propylene and a set amount of hydrogen at room temperature, and heat to 70°C.

[0113] Step 2: Before the reactor temperature reaches 70°C, 2.0 mL of 0.5 M alkylaluminum heptane solution, 0.4 mL of 0.5 M D-donor hexane solution and 6.0 mg of the above catalyst component 1# are pre-complexed for 5 min. When the reactor reaches 70°C, the mixture is injected into the reactor to start the reaction.

[0114] Step 3: After reacting for 60 minutes, vent the material, cool down, and stop the reaction. The polypropylene resin is then removed and vacuum dried at 30°C for 2 hours. The resulting polypropylene product is then tested for melt flow rate (MFR), xylene-soluble content (XS), and GPC. Specific hydrogen addition amounts and test results are shown in Table 1 below.

[0115] Polymerization Example b1:

[0116] The difference from polymerization example a1 lies in the amount of hydrogen added. The specific amount of hydrogen added and the test results are shown in Table 1 below.

[0117] Polymerization Examples a2-a14:

[0118] The difference from polymerization example a1 is that catalyst component 1# was replaced with catalyst components 2#-14# respectively. Specific test results are shown in Table 1 below.

[0119] Polymerization Examples b2-b14:

[0120] The difference from polymerization example b1 is that catalyst component 1# was replaced with catalyst components 2#-14# respectively. Specific test results are shown in Table 1 below.

[0121] Polymerization Comparative Examples a1-a4:

[0122] The difference from polymerization example a1 is that catalyst component 1# was replaced with catalyst components C1#-C4# respectively. Specific test results are shown in Table 1 below.

[0123] Polymerization Comparative Examples b1-b4:

[0124] The difference from polymerization example b1 is that catalyst component 1# was replaced with catalyst components C1#-C4# respectively. Specific test results are shown in Table 1 below.

[0125] Table 1

[0126]

[0127]

[0128] The polymerization results in Table 1 show that the catalyst prepared using the internal electron donor of this invention exhibits excellent activity and low xylene solubility when used for propylene polymerization. Under the same preparation process, the catalyst prepared using the internal electron donor modified with adamantane and norborneol is more sensitive to hydrogen regulation, and hydrogen has a lower impact on xylene solubility.

Claims

1. An internal electron donor compound for use as a catalyst in olefin polymerization, said internal electron donor compound having the structure shown in Formula I: In formula I, G has 4-30 carbon atoms and is a substituted or unsubstituted alkyl group containing at least two rings, a heteroaryl group containing at least two rings and heteroatom-substituted alkyl group, or an amino group containing at least two rings; R1-R3 may be the same or different, and each is independently selected from H, halogen, C2-C18 alkenyl, C1-C18 substituted or unsubstituted straight-chain alkyl or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, and two or more of R1-R3 may bond to each other to form a ring or an unsaturated bond. A and B may be the same or different, and each is independently selected from ester group, amino group, amide group, sulfonyl ester group and sulfonamide group; in, The substituents used for substitution are rare earth groups, halogens, or heteroatoms; the heteroatoms are selected from N, O, S, P, and Si.

2. The internal electron donor compound according to claim 1, characterized in that, The ester group is selected from R4COO-, R5OOC-, and R6R7NCOO-; the amino group is selected from R6R7N-; the amide group is selected from R8CONR9- and R 10 R 11 NCO-; the sulfonyl ester group is selected from R 12 SO3-; the sulfonamide group is selected from R 11 SO2R 13 N-; where R4-R 13 They may be the same or different, and are each independently selected from H, halogen, C2-C18 alkenyl, C1-C18 substituted or unsubstituted straight-chain alkyl or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indene, benzyl.

3. The internal electron donor compound according to claim 2, characterized in that, In Formula I, G has the structure of adamantyl, norbornel, N,N-dicyclopentylamino, or carbazolyl.

4. The internal electron-donating compound according to any one of claims 1-3, characterized in that, The internal electron donor compound is selected from the following compounds:

5. A catalyst component for olefin polymerization, characterized in that, The catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor compound according to any one of claims 1-4.

6. The catalyst component according to claim 5, characterized in that, During the preparation of the catalyst component, the magnesium compound and titanium compound are contacted with the internal electron donor compound to obtain the catalyst component; wherein, the magnesium compound is magnesium halide or magnesium diethoxy; the titanium compound is TiXn(OR)4-n, where R is a hydrocarbon group with 1-20 carbon atoms, X is a halogen, and n = 1-4; preferably titanium tetrachloride; Preferably, the ratio of the internal electron donor compound, the magnesium compound, and the titanium compound is 1:(5-50):(20-500).

7. The catalyst component according to claim 6, characterized in that, The preparation process of the catalyst component is as follows: In a stirred reactor with a filter function, fully purged with nitrogen, 2-2.5 parts by weight of magnesium diethoxy and 50-60 parts by weight of chlorobenzene are added. Then, 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution are added dropwise while maintaining at room temperature. The temperature is then raised to 85-95°C, and 1-2 parts by weight of the internal electron donor compound are added. The temperature is further raised to 100-120°C and reacted for 0.5-2 hours. Solid-liquid separation is then performed. Another 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added, and the reaction continues at 100-120°C for 0.5-2 hours. After solid-liquid separation again, another 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added, and the reaction is carried out at 100-120°C for 15-45 minutes. After solid-liquid separation, the mixture is washed with n-heptane and dried to obtain the catalyst component. The volume ratio of titanium tetrachloride to chlorobenzene in the titanium tetrachloride / chlorobenzene solution is (4:6)-(6:4).

8. A method for olefin polymerization, wherein the method comprises polymerizing olefin monomers to form a polymer in the presence of a catalyst obtained by reacting an organoaluminum compound, a siloxane compound, and a catalyst component according to any one of claims 4-7.

9. The method according to claim 8, characterized in that, The olefin is propylene, and the method includes: Step 1: Purge the reactor with nitrogen, then add liquid propylene and hydrogen sequentially at room temperature, and heat to the set temperature; Step 2: The heptane solution of the organoaluminum compound, the hexane solution of the siloxane compound (as an external electron donor), and the catalyst component according to any one of claims 6-8 are mixed and reacted to form a catalyst. When the reaction vessel reaches the set temperature, the mixture is injected into the reaction vessel to start the reaction and obtain the polymer. The set temperature is 65-75℃; The ratio of the catalyst component, organoaluminum compound, and siloxane compound is 1:(5-200):(5-50).

10. The method according to claim 9, characterized in that, The organoaluminum compound is a trialkylaluminum compound, preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trioctylaluminum or methylaluminoxane; The siloxane compound of the external electron donor is dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, or dimethoxydiphenylsilane; preferably, the siloxane compound is dicyclopentyldimethoxysilane.

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