Internal electron donor compound, catalyst component and olefin polymerization method

Abstract

An internal electron donor compound, a catalyst component and an olefin polymerization method. The internal electron donor compound has structural formula (I) as shown below. In the formula, R0 is C or D, wherein C is selected from H, halogen, a cyano group, saturated or unsaturated C1-C10 linear or branched alkyl, cycloalkyl, alkenyl, an ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, and halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl and benzyl, the heteroatom being selected from N, O, S, P and Si, or C is selected from a heteroaryl substituent, and D has 4-30 carbon atoms, and is substituted or unsubstituted alkyl containing at least two rings, heteroatom-substituted heteroaryl containing at least two rings or an amino group containing at least two rings; R1-R3 are the same or different, and are each independently selected from H, halogen, C2-C18 alkenyl, C1-C18 substituted or unsubstituted linear or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl and benzyl, and two or more of R1-R3 can be bonded to each other to form a ring or an unsaturated bond; A and B are the same or different, and are each independently selected from an ester group, an amino group, an amide group, a sulfonyl ester group and a sulfonamide group; a substituent used for substitution is alkenyl, halogen or a heteroatom, and the heteroatom is selected from N, O, S, P and Si; and when R0 is C, R1 and R2 are bonded to each other to form a ring, A is an ester group connected to the parent benzene ring by means of a hydroxyl group, and B is an ester group connected to the parent benzene ring by means of a carboxyl group. The catalyst prepared from the internal electron donor exhibits very high catalytic activity and hydrogen sensitivity in olefin polymerization.

Description

Internal electron donor compound, catalyst component and olefin polymerization method TECHNICAL FIELD

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

[0002] It is well known that 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-use 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 response 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 response 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] CN1257920C and US61141902A use salicylate and 1,2-phenylene aromatic diester compounds as internal electron donors of propylene polymerization catalyst, but do not realize the importance of group substitution on the benzene ring. CN104829757B and US61141902A make some simple substitutions on the benzene ring, but the activity and stereoselectivity and hydrogen regulation ability of the catalyst still have room for further improvement.

[0006] Phthalate compounds as plasticizer substances have attracted more and more attention on the potential harm to human health, which also limits its use in Ziegler-Natta catalyst; secondly, different internal electron donors have a significant impact on the performance of Ziegler-Natta catalyst, and by developing different internal electron donors to obtain high-efficiency catalysts with different functions, which is of great importance to the further development of polyolefin industry.

[0007] 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

[0008] The purpose of the present application is to provide an internal electron donor compound, a catalyst component and an olefin polymerization method to improve the catalytic activity of the catalyst in olefin polymerization.

[0009] To achieve the above-mentioned purpose of the application, the internal electron donor compound of the present application adopts the following technical scheme:

[0010] An internal electron donor compound for a catalyst for olefin polymerization, the internal electron donor compound has the following structure:

[0011] In the formula,

[0012] R0 is C or D; wherein C is selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight chain alkyl or branched alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from heterocyclic aryl substituents; D has a carbon number of 4-30, and is a substituted or unsubstituted alkyl containing at least two rings, a heteroatom-substituted heteroaryl containing at least two rings, an amino group containing at least two rings;

[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 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, amino, amide, sulfonyl ester and sulfonyl amide;

[0015] wherein the substituent for substitution is rare base, halogen or heteroatom; the heteroatom is selected from N, O, S, P, Si;

[0016] wherein R0 is C, R1 and R2 are bonded to each other to form a ring, and A is an ester connected to the benzene ring of the same nucleus through a hydroxyl group, and B is an ester connected to the benzene ring of the same nucleus through a carboxyl group.

[0017] In the internal electron donor compound of the present application, the ester can be R4COO-, R5OOC- or R6R7NCOO-; the amino can be R6R7N-; the amide can be R8CONR9- or R 10 R 11 NCO-; the sulfonyl ester can be R 12 SO3-; the sulfonyl amide can be 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 straight chain alkyl or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; wherein the substituent for substitution is rare base, halogen or heteroatom; the heteroatom is selected from N, O, S, P, Si.

[0018] In the internal electron donor compound of the present application, the C2-C18 alkenyl can be exemplified by C3-C15 rare base, C5-C13 rare base, C6-C11 rare base or C8-C10 rare base.

[0019] In the internal electron donor compound of the present application, the C1-C18 substituted or unsubstituted straight chain alkyl or branched alkyl can be exemplified by C2-C15, C4-C13, C6-C11 or C8-C10 substituted or unsubstituted straight chain alkyl or branched alkyl.

[0020] In the internal electron donor compound of the present application, the C1-C10 straight chain alkyl or branched alkyl can be exemplified by C2-C9, C3-C8, C4-C7 or C5-C6 substituted or unsubstituted straight chain alkyl or branched alkyl.

[0021] In the internal electron donor compound of the present application, "halogen or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl" refers to hydrogen atoms or carbon atoms in alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl and benzyl being substituted by halogen or heteroatom.

[0022] In some embodiments, the internal electron donor compound has the following structure of formula I:

[0023] In formula I,

[0024] G has a carbon number of 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 a cycloalkyl group, a heteroatom-substituted heteroaryl group containing at least two rings, an amino group containing at least two rings, such as two Hs on the amino group being substituted by one ring respectively, for example, a five-membered ring or a six-membered ring, wherein it is understood in the art that the two rings on the amino group can also be connected by a carbon-carbon bond, thereby further forming a nitrogen heterocycle;

[0025] 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;

[0026] A and B are the same or different, each independently selected from an ester group, an amino group, an amide group, a sulfonyl ester group and a sulfonyl amide group;

[0027] wherein the substituent for substitution is a rare group, a halogen or a heteroatom; the heteroatom is selected from N, O, S, P and Si.

[0028] It is found that, for the internal electron donor compound of formula I, after the G position is modified by a polycyclic 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.

[0029] In some embodiments, in formula I, the ester group in A and B 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-; and the sulfonyl amide group is selected from R 11 SO2R 13 N-; wherein R4-R13 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 halogen, or heteroatoms selected from N, O, S, P, Si.

[0030] In Formula I of the present application, G has a carbon number of 4-30, such as 6, 8, 10, 20, or 25, and contains two, three, four, or more five-membered and / or six-membered rings, such as cycloalkyl or aryl; in some embodiments, carbons in the meta- or para- position of a single ring can be connected by linear or branched alkyl to form multiple rings.

[0031] In preferred embodiments, G in Formula I has the structure adamantyl, norbornyl, N,N-dicyclopentylamino, or carbazolyl, preferably adamantyl or norbornyl, and the catalyst prepared with such modified internal electron donor is more sensitive to hydrogen adjustment and has lower hydrogen effect on xylene solubles.

[0032] In preferred embodiments, the internal electron donor compound is selected from the following compounds:

[0033] In some embodiments, the internal electron donor compound has the structure shown in Formula II:

[0034] In Formula II,

[0035] Ra-Re are the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from heterocyclic aryl substituents;

[0036] two or more of Ra-Re are bonded to each other or not to each other into a ring or into an unsaturated bond;

[0037] m and n are each an integer from 0 to 8, such as 1, 2, 3, 4, 5, 6, or 7.

[0038] The research found that for the internal electron donor of the structure shown in formula II, after the ring modification at the 3-4 position of salicylic acid, the derived compound is used as the internal electron donor of Ziegler-Natta catalysis, the prepared catalyst shows higher catalytic activity and hydrogen regulation sensitivity in olefin polymerization, and the prepared polymer has the characteristics of relatively lower xylene solubles and wider molecular weight distribution.

[0039] In some embodiments, the internal electron donor compound has the structure shown in formula II-1 as follows:

[0040] In formula II-1,

[0041] R1-R 10 are the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from a heterocyclic aryl substituent;

[0042] Two or more of R1-R8 are bonded to each other or not to form a ring or an unsaturated bond.

[0043] In some embodiments, the internal electron donor compound has the structure shown in formula II-2 as follows:

[0044] In formula II-2,

[0045] R1-R 12 are the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from a heterocyclic aryl substituent;

[0046] R1-R 10 Two or more of R1-R8 are bonded to each other or not to form a ring or an unsaturated bond.

[0047] In some embodiments, the internal electron donor compound has the structure shown in formula II-3 as follows:

[0048] In formula II-3,

[0049] R1-R8are the same or different, each independently selected from the group consisting of H, halogen, cyano, saturated or unsaturated C1-C10 linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from a heterocyclic aryl substituent;

[0050] two or more of R1-R6are bonded to each other or not to each other to form a ring or an unsaturated bond.

[0051] In some embodiments, the internal electron donor compound is selected from the group consisting of:

[0052] To achieve the above object of the present application, the catalyst component of the present application employs the following technical solution:

[0053] A catalyst component for the polymerization of olefins, said catalyst component comprising a titanium compound, a magnesium compound and an internal electron donor compound as described above.

[0054] 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: XnMg(OR) 2-n MgCl2.mROH, MgCl2 / SiO2, MgCl2 / Al2O3, or a mixture of magnesium halide and titanium alkoxide, wherein m is 1-6, 0≦n≦2, X is halogen, and R is hydrogen or C1-C8 hydrocarbon group; preferably, the magnesium compound is magnesium halide or diethoxy magnesium.

[0055] In the present application, the precursor of the magnesium halide can be XnMg(OEt) 2- n, MgCl2.mEtOH, wherein m is 1-6, 0≦n≦2, and X is halogen.

[0056] In some embodiments, the general formula of the titanium compound is TiXn(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.

[0057] 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; the internal electron donor compound, the magnesium chloride precursor and the titanium compound can be used in a ratio of 1 : (5-50) : (20-500), for example, 1 part by weight of the internal electron donor compound, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45 or 50 parts by weight of the magnesium halide precursor, and 20, 40, 60, 100, 200, 300, 400 or 500 parts by weight of the titanium compound.

[0058] In a preferred embodiment, the catalyst component is prepared as follows:

[0059] In a reactor with filtration function with stirring, which is sufficiently replaced by nitrogen, 2-2.5 parts by weight, such as 2.1, 2.2, 2.2 or 2.4 parts by weight of diethoxy magnesium and 50-60 parts by weight, such as 52, 55 or 58 parts by weight of chlorobenzene are added, then 120-160 parts by weight, such as 130, 140 or 150 parts by weight of titanium tetrachloride / chlorobenzene solution is added dropwise at room temperature, then the temperature is raised to 85-95°C, such as 88, 90 or 92°C, 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, the temperature is continuously raised to 100-120°C, such as 105, 110 or 115°C, and reacted for 0.5-2 hours, such as 1 or 1.5 hours, then solid-liquid separation is performed, then 120-160 parts by weight, such as 130, 140 or 150 parts by weight of titanium tetrachloride / chlorobenzene solution is added again, and reacted for 0.5-2 hours, such as 1 or 1.5 hours, at 100-120°C, such as 105, 110 or 115°C, then solid-liquid separation is performed again, then 120-160 parts by weight, such as 130, 140 or 150 parts by weight of titanium tetrachloride / chlorobenzene solution is added again and reacted for 15-45 minutes, such as 20, 30, 35 or 40 minutes, at 100-120°C, such as 105, 110 or 115°C, then solid-liquid separation is performed, 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.

[0060] In another aspect to achieve the above-mentioned object, the olefin polymerization method of the present application uses the following technical solution:

[0061] An olefin polymerization method, wherein the olefin monomer is polymerized in the presence of an organic aluminum compound, a siloxane compound and a catalyst obtained by reacting the above-mentioned catalyst component to form a polymer; preferably, the olefin is propylene.

[0062] In one embodiment, the method comprises:

[0063] Step 1, replace the reactor with nitrogen, then sequentially add liquid propylene and hydrogen at room temperature, and heat to the set temperature;

[0064] Step 2, mix the heptane solution of the organoaluminum compound, the hexane solution of the siloxane compound as external electron donor, and the above catalyst component to react, then inject the mixture into the reactor to start the reaction when the reactor reaches the set temperature, to obtain the polymer;

[0065] The set temperature is 65-75℃, such as 68, 70, or 72℃.

[0066] In some embodiments, the usage ratio between the catalyst component, the organoaluminum compound, and the siloxane compound is 1:(5-200):(5-50), such as 1 part by weight of the catalyst component, 5, 10, 20, 50, 100, 150, or 200 parts by weight of the organoaluminum compound, and 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by weight of the siloxane compound.

[0067] In some embodiments, the organoaluminum compound has the general formula AlR n X (3-n) , wherein R is hydrogen or a hydrocarbon group with 1-20 carbon atoms; X is halogen, and n is an integer of 0≦n≦3; preferably, the organoaluminum compound is a trialkyl aluminum compound, preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, trioctyl aluminum, or methylaluminoxane.

[0068] 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 of 0≦n≦3, such as 1 or 2; the external electron donor siloxane compound is dicyclopentyl dimethoxysilane, cyclohexyl methyl dimethoxysilane, or dimethoxy diphenyl silane; preferably, the siloxane compound is dicyclopentyl dimethoxysilane.

[0069] Compared with the prior art, the present application has the following advantages:

[0070] When the internal electron donor of the present application is used in Ziegler-Natta catalysis, the prepared catalyst shows very high catalytic activity and hydrogen sensitivity in olefin polymerization; the prepared polymer has relatively low xylene solubles and a wide molecular weight distribution. DETAILED DESCRIPTION

[0071] For the purpose of understanding the present application, the present application will be further described with reference to the following examples. It should be understood that these examples are intended to be illustrative only and are not intended to limit the scope of the present application.

[0072] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges are provided as example of the boundaries of the ranges. The endpoints of the ranges can be modified by the use of "about" or "approximately," and the ranges can be modified by the use of "substantially" or "approximately." The disclosure herein also contemplates that when any of the ranges are used herein, all values and sub-ranges within the range are intended to be included. For example, if a range of "1 to 5" is disclosed, then all values and sub-ranges between (and including) 1 and 5 are also disclosed. The statement of a range can be used as a basis for claiming a range of values. For example, a range of "1 to 5" can be used to claim 1, 2, 3, 4, or 5 individually, or 1-5, 1-4, 1-3, 1-2, 2-5, 3-5, or 2-4 individually, or any other combination of the individual numbers.

[0073] 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 application belongs. The term "and / or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.

[0074] Unless otherwise indicated, the following examples / Comparative Examples were prepared according to the following experimental procedures. Unless otherwise indicated, the reagents or instruments used were conventional products available on the market.

[0075] <Source of raw materials>

[0076] 3-methyl-5-adamantyl-1,2-dihydroxybenzene was purchased from Inokem;

[0077] 3-methyl-5-adamantyl-2-hydroxybenzoic acid was purchased from BLD Pharmatech Co., Ltd;

[0078] 2,3-dihydro-4-hydroxy-7-adamantyl-1H-indene-5-carboxylic acid was purchased from BLD Pharmatech Co., Ltd;

[0079] 4-adamantyl-5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid was purchased from Aldrich Reagent;

[0080] 4-adamantyl-1-hydroxy-2-naphthoic acid was purchased from BLD Pharmatech Co., Ltd;

[0081] 3-methyl-5-adamantyl-2-benzyloxybenzoic acid was purchased from Inokem;

[0082] 3-methyl-5-(dicyclopentylamino)-2-hydroxybenzoic acid was purchased from BLD Pharmatech Co., Ltd;

[0083] 3-methyl-5-(9-carbazolyl)-2-hydroxybenzoic acid, purchased from Sigma-Aldrich;

[0084] 4-norbornyl-1-amino-2-benzoic acid, purchased from National Pharmaceutical Group;

[0085] 2,3-dihydro-7-adamantyl-4,5-hydroxy-1H-indene, purchased from Inokai;

[0086] 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid, purchased from Inokai;

[0087] 2,3-dihydro-4-hydroxy-1H-indene-5-carboxylic acid, purchased from Inokai;

[0088] 2,3-dihydro-4-hydroxy-7-tert-butyl-1H-indene-5-carboxylic acid, purchased from Inokai;

[0089] 2,2-dimethyl-3-hydro-4-hydroxy-7-tert-butyl-1H-indene-5-carboxylic acid, purchased from Inokai;

[0090] 2,2-dimethyl-3-hydro-4-hydroxy-7-tert-butyl-1-methylindene-5-carboxylic acid, purchased from Inokai;

[0091] 1,2,3,6,7,8-hexahydro-5-hydroxy-as-benzodihydroindene-4-carboxylic acid, purchased from Inokai;

[0092] 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid, replaced with 1-hydroxy-2-naphthoic acid, purchased from Inokai;

[0093] 1-hydroxy-4-tert-butyl-2-naphthoic acid, purchased from Inokai;

[0094] 2-methyl-5-tert-butyl-2-hydroxybenzoic acid, purchased from Inokai;

[0095] 2,3-dihydro-4-hydroxy-7-tert-butyl-1H-indene-5-carboxylic acid, purchased from Inokai;

[0096] triethylamine, purchased from National Pharmaceutical Group;

[0097] benzoyl chloride, purchased from National Pharmaceutical Group;

[0098] dichloromethane, purchased from National Pharmaceutical Group;

[0099] diethyl ether, purchased from National Pharmaceutical Group;

[0100] methanesulfonyl chloride, purchased from National Pharmaceutical Group;

[0101] benzenesulfonyl chloride, purchased from National Pharmaceutical Group;

[0102] N,N-diethylaminocarbonyl chloride, purchased from Sigma-Aldrich.

[0103] <TEST METHODS>

[0104] The polymer related data in the following examples / Comparative Examples were obtained according to the following test methods:

[0105] 1. Melt flow rate MFR: measured according to ASTM D1238;

[0106] 2. Xylene solubles XS: measured using a fully automated Xylene Solubles Determinator (CRYSTEX QC) from Polymer Char;

[0107] 3. Molecular weight and its distribution: measured using a High Temperature Gel Permeation Chromatograph (GPC-IR6) from Polymer Char;

[0108] 4. Activity: weight of product per hour catalyzed per gram of catalyst.

[0109] In the following first group of examples / Comparative Examples, the internal electron donors used are described as follows:

[0110] (ID1) Chemical name: 3-methyl-5-adamantyl-1,2-dibenzoyloxybenzene

[0111] The preparation method is as follows:

[0112] Into a 500 mL flask, 3-methyl-5-adamantyl-1,2-dihydroxybenzene 25.8 g (100 mmol) and triethylamine about 30 g (3 eq) were added, and about 300 mL of DCM (dichloromethane) was added. Stirring at room temperature, 32 g (2.2 eq) of benzoyl chloride was slowly added to the flask, stirring at room temperature for about 5 h until the reaction was complete. The reaction was transferred to a 1000 mL flask, and the DCM was removed by rotary evaporation at room temperature. After completion, 150 mL of ether and 200 mL of water were added to the flask, and extraction was carried out in a separatory funnel. The organic phase was separated, washed with 200 mL of water twice. Then dried with anhydrous sodium sulfate, and the organic phase was obtained by suction filtration, and the organic phase was rotary evaporated to obtain a light yellow solid. Then recrystallized with ethyl acetate / petroleum ether (1:20) to obtain white solid product, yield 89%.

[0113] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0114] (ID2) Chemical name: n-butyl 3-methyl-5-adamantyl-2-benzyloxybenzoate

[0115] The preparation method is as follows:

[0116] In a 500 mL flask, 3-methyl-5-adamantyl-2-hydroxybenzoic acid 28.6 g (100 mmol) and about 300 mL of DCM and 20 mL of THF (tetrahydrofuran) were added and stirred at room temperature, 25 g of DCC (dicyclohexyl carbodiimide) was slowly added, after stirring at room temperature for 2 h, 15 g of n-butanol was slowly added dropwise into the reaction system, and stirring was continued at room temperature for 5 h, filtration, and the organic phase was concentrated to obtain n-butyl 3-methyl-5-adamantyl-2-hydroxybenzoate.

[0117] The obtained product was dissolved in about 300 mL of DCM, 30 g (3 eq) of triethylamine was added, 17 g (1.2 eq) of benzoyl chloride was slowly added under ice water bath condition, and stirring was continued at room temperature for 2 h after dropwise addition, filtration, and the organic phase was concentrated, and the target compound was recrystallized from ethyl acetate / petroleum ether (1:50) with a yield of 78%.

[0118] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0119] (ID3) Chemical name: isobutyl 3-methyl-5-adamantyl-2-benzyloxybenzoate

[0120] ID3 was prepared by the same method as ID2, except that n-butanol was replaced by isobutanol.

[0121] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 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.

[0122] (ID4) Chemical name: 2,3-dihydro-4-benzoyloxy-7-adamantyl-1H-indene-5-carboxylic acid n-butyl ester

[0123] ID4 was prepared by the same method as ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid was replaced by 2,3-dihydro-4-hydroxy-7-adamantyl-1H-indene-5-carboxylic acid.

[0124] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 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.

[0125] (ID5) Chemical name: 4-adamantyl-5,6,7,8-tetrahydro-1-benzoyloxy-2-naphthoic acid isobutyl ester

[0126] ID5 was prepared by the same method as ID2, except that 3-methyl-5-adamantyl-2-hydroxybenzoic acid was replaced by 4-adamantyl-5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid, and n-butanol was replaced by isobutanol.

[0127] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0128] (ID6) Chemical name: 4-Adamantyl-1-benzoyloxy-2-naphthoic acid n-butyl ester

[0129] ID6 was prepared according to the procedure of ID2, except that 3-methyl-5- adamantyl-2-hydroxybenzoic acid was replaced by 4-adamantyl-1-hydroxy-2- naphthoic acid.

[0130] 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0131] (ID7) Chemical name: 3-Methyl-5-bornyl-2-benzoyloxybenzoic acid isobutyl ester

[0132] ID7 was prepared according to the procedure of ID2, except that 3-methyl-5- adamantyl-2-hydroxybenzoic acid was replaced by 3-methyl-5-bornyl-2- benzoyloxybenzoic acid and n-butanol was replaced by isobutanol.

[0133] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0134] (ID8) Chemical name: 3-methyl-5-(dicyclopentylamino)-2-benzoyloxybenzoic acid isobutyl ester

[0135] ID8 was prepared according to the same procedure as ID2, except that 3-methyl-5- adamantyl-2-hydroxybenzoic acid was replaced by 3-methyl-5-(dicyclopentylamino)-2- hydroxybenzoic acid and n-butanol was replaced by isobutanol.

[0136] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0137] (ID9) Chemical name: 3-methyl-5-(9-carbazolyl)-2-benzoyloxybenzoic acid isobutyl ester

[0138] ID9 was prepared according to the same procedure as ID2, except that 3-methyl-5- adamantyl-2-hydroxybenzoic acid was replaced by 3-methyl-5-(9-carbazolyl)-2- hydroxybenzoic acid and n-butanol was replaced by isobutanol.

[0139] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0140] (ID10) Chemical name: 4-norbornyl-1-benzoyloxy-2-phenylcarbonyloxy isobutyl

[0141] ID10 is prepared according to the procedure of ID2, except that 3-methyl-5- adamantyl-2-hydroxybenzoic acid is replaced by 4-norbornyl-1-amino-2- benzoic acid and n-butanol is replaced by isobutanol.

[0142] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0143] (ID11) Chemical name: 2,3-dihydro-7-adamantyl-4,5-dibenzoyloxy-1H-indene

[0144] ID11 is prepared according to the procedure of ID1, except that 3-methyl-5- adamantyl-1,2-hydroxybenzene is replaced by 2,3-dihydro-7-adamantyl-4,5- hydroxy-1H-indene.

[0145] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0146] (ID12) Chemical name: 3-methyl-5-adamantyl- 1,2-dimethanesulfonyloxybenzene The preparation method of ID12 is the same as that of ID1, except that benzoyl chloride is replaced by methanesulfonyl chloride.

[0147] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0148] (ID13) Chemical name: 3-methyl-5-adamantyl- 1,2-diphenylsulfonyloxybenzene

[0149] The preparation method of ID13 is the same as that of ID1, except that benzoyl chloride is replaced by phenylsulfonyl chloride.

[0150] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0151] (ID14) Chemical name: 3-methyl-5-adamantyl- 1,2-diphenylsulfonyloxybenzene

[0152] The preparation method of ID14 is the same as that of ID1, except that benzoyl chloride is replaced by N,N-diethylaminocarbonyl chloride.

[0153] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0154] (C1) DNBP, chemical name: di-n-butyl phthalate; from JP62158704 A;

[0155] (C2) Chemical name: 3-methyl-5-tert-butyl-1,2-dibenzoyloxybenzene, from WO2010078485 A1;

[0156] (C3) Chemical name: n-butyl 3-methyl-5-tert-butyl-2-benzoyloxybenzoate;

[0157] The preparation method of C3 is the same as ID15 below, except that 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid is replaced by 3-methyl-5-tert-butyl-2-hydroxybenzoic acid;

[0158] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0159] (C4) Chemical name: 2,3-dihydro-4-benzoyloxy-7-tert-butyl-1H-indene-5-carboxylic acid isobutyl ester (i.e. ID17 below).

[0160] Preparation of catalyst component Example A1

[0161] In a 250 ml nitrogen-purged reactor with stirring and filtration function, 2.2 g of diethoxy magnesium and 50 mL of chlorobenzene were added, then 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio 1:1) was added dropwise at room temperature, then slowly heated to 90°C, 1.5 g of ID1 was added, then heated to 110°C and kept for 1 hour, then the liquid was filtered clean, the liquid was filtered off, then 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio 1:1) was added again, reacted at 110°C for 1 hour, the liquid was filtered clean, 100 mL of n-heptane was added to wash the solid, repeated three times, the liquid was filtered off and dried, and the solid powder was the prepared catalyst component 1#. The titanium content, internal donor content and polymerization data of catalyst component 1 are shown in Table 1 below.

[0162] Catalyst component preparation examples A2-A14

[0163] The difference from catalyst component preparation example Al is that the internal donor ID1 is replaced by ID2-ID14 accordingly, and the addition of titanium tetrachloride is adjusted accordingly. The titanium content, internal donor content and polymerization data of the prepared catalyst components 2#-14# are shown in Table 1 below.

[0164] Catalyst component preparation comparative examples A1-A4

[0165] The difference from catalyst component preparation example Al is that the internal donor ID1 is replaced by C1-C4 accordingly, and the addition of titanium tetrachloride is adjusted accordingly. The titanium content, internal donor content and polymerization data of the prepared catalyst components C1#-C4# are shown in Table 1 below.

[0166] Polymerization example a1:

[0167] Propylene polymerization was carried out on a laboratory 5L stainless steel polymerization kettle:

[0168] Step one, first purging the reactor with refined nitrogen (water content <1 ppm, oxygen content <1 ppm); then sequentially adding 2.2 L of liquid propylene and a set amount of hydrogen at room temperature, and heating to 70°C;

[0169] Step two, before the temperature of the reactor reaches 70°C, 2.0 mL of 0.5M alkyl aluminum heptane solution, 0.4 mL of 0.5M D-donor hexane solution and 6.0 mg of the above catalyst component 1# were pre-complexed for 5 min, then the mixture was injected into the reactor to start the reaction when the reactor reached 70°C;

[0170] Step three, after 60 min of reaction, the material was discharged, cooled, and the reaction was stopped. The polypropylene resin was removed and vacuum dried at 30°C for 2 h. The obtained polypropylene product was tested for melt flow rate (MFR), xylene solubles (XS), GPC, etc. The specific hydrogen addition amount and test results are shown in Table 1 below.

[0171] Polymerization Example b1:

[0172] The difference from Polymerization Example a1 is that the hydrogen addition amount is different. The specific hydrogen addition amount and test results are shown in Table 1 below.

[0173] Polymerization Examples a2-a14:

[0174] The difference from Polymerization Example a1 is that the catalyst component 1# is replaced by catalyst components 2#-14#, respectively. The specific test results are shown in Table 1 below.

[0175] Polymerization Examples b2-b14:

[0176] The difference from Polymerization Example b1 is that the catalyst component 1# is replaced by catalyst components 2#-14#, respectively. The specific test results are shown in Table 1 below.

[0177] Polymerization Comparative Examples a1-a4:

[0178] The difference from Polymerization Example a1 is that the catalyst component 1# is replaced by catalyst components C1#-C4#, respectively. The specific test results are shown in Table 1 below.

[0179] Polymerization Comparative Examples b1-b4:

[0180] The difference from Polymerization Example b1 is that the catalyst component 1# is replaced by catalyst components C1#-C4#, respectively. The specific test results are shown in Table 1 below.

[0181] Table 1

[0182] The polymerization results in Table 1 show that the catalyst prepared using the internal electron donor of the application has excellent activity and lower xylene solubles when used for propylene polymerization. Under the same preparation process, the catalyst prepared using the internal electron donor containing adamantane and norbornane modification is more sensitive to hydrogen adjustment, and the effect of hydrogen on xylene solubles is lower.

[0183] In the following second group of examples / comparative examples, the internal electron donors used are described as follows:

[0184] (ID15) Chemical name: 5,6,7,8-tetrahydro-1-benzoyloxy-2-naphthalene carboxylic acid n-butyl ester

[0185] The preparation method is as follows:

[0186] In a 500 mL flask, 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid 19 g (100 mmol) and about 300 mL of DCM (dichloromethane) and 20 mL of THF (tetrahydrofuran) were added and stirred at room temperature, 25 g of DCC (dicyclohexyl carbodiimide) (1.2 eq) was slowly added, after the addition was completed, it was stirred at room temperature for 2 h, then 15 g of n-butanol was slowly added dropwise into the reaction system, and the stirring was continued at room temperature for 5 h, then it was filtered, and the organic phase was concentrated to obtain n-butyl 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoate.

[0187] The obtained product was dissolved in about 300 mL of DCM, 30 g (3 eq) of triethylamine was added, 17 g (1.2 eq) of benzoyl chloride was slowly added dropwise under ice water bath condition, after the dropwise addition was completed, it was stirred at room temperature for 2 h, then it was filtered, the organic phase was concentrated, and the target compound was recrystallized from ethyl acetate / petroleum ether (1:50) with a yield of 83%.

[0188] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ (ppm) 8.23-8.21 (2H), 7.86 (1H), 7.63-7.61 (1H), 7.58-7.46 (3H), 3.93-3.92 (2H), 2.90-2.85 (4H), 2.15-2.01 (4H), 1.41-1.37 (2H), 1.27-1.21 (2H), 0.77-0.74 (3H); LC-MS (m / z) (M+): 352.24.

[0189] (ID16) Chemical name: n-butyl 2,3-dihydro-4-benzyloxy-1H-indene-5-carboxylate

[0190] The preparation method of ID16 is the same as that of ID15, except that 5,6,7,8-tetrahydro-1-hydroxy-2-naphthoic acid is replaced by 2,3-dihydro-4-hydroxy-1H-indene-5-carboxylic acid.

[0191] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, TMS): δ (ppm) 8.23-8.21 (2H), 7.86 (1H), 7.63-7.61 (1H), 7.58-7.46 (3H), 3.93-3.92 (2H), 2.90-2.87 (4H), 2.15-2.10 (2H), 1.41-1.37 (2H), 1.27-1.21 (2H), 0.77-0.74 (3H); LC-MS (m / z) (M+): 338.19.

[0192] (ID17) Chemical name: 2,3-dihydro-4-benzyloxy-7-tert-butyl-lH-indene-5-carboxylic acid isobutyl ester

[0193] ID17 was prepared according to the procedure of ID15, except that 5,6,7,8-tetrahydro-l-hydroxy-2-naphthoic acid was replaced by 2,3-dihydro-4-hydroxy-7-tert-butyl-lH-indene-5-carboxylic acid.

[0194] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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.

[0195] (ID18) Chemical name: 2,2-dimethyl-3-hydro-4-benzyloxy-7-tert-butyl-lH-indene-5-carboxylic acid isobutyl ester

[0196] ID18 was prepared according to the procedure of ID15, except that 5,6,7,8-tetrahydro-l-hydroxy-2-naphthoic acid was replaced by 2,2-dimethyl-3-hydro-4-hydroxy-7-tert-butyl-lH-indene-5-carboxylic acid.

[0197] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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), 3.07 (2H), 2.59 (2H), 1.73-1.70 (1H), 0.83-0.81 (21H); LC-MS (m / z) (M+): 423.42.

[0198] (ID19) Chemical name: 2,2-dimethyl-3-hydro-4-benzyloxy-7-tert-butyl-1-methylindene-5- carboxylic acid isobutyl ester

[0199] ID19 is prepared according to the procedure of ID15, except that 5,6,7,8-tetrahydro-1- hydroxy-2-naphthoic acid is replaced by 2,2-dimethyl-3-hydro-4-hydroxy-7-tert-butyl-1- methylindene-5-carboxylic acid.

[0200] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, 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), 3.07 (2H), 2.59 (1H), 1.73-1.70 (1H), 0.83-0.81 (24H); LC-MS (m / z) (M+): 436.31.

[0201] (ID20) Chemical name: 1,2,3,6,7,8-hexahydro-5-benzyloxy-as-benzodiinde-4-carboxylic acid isobutyl ester

[0202] ID20 is prepared according to the procedure of ID15, except that 5,6,7,8-tetrahydro-1- hydroxy-2-naphthoic acid is replaced by 1,2,3,6,7,8-hexahydro-5-hydroxy-as-benzodiinde-4- carboxylic acid.

[0203] 1H NMR and LC-MS (m / z) (M+) data are as follows: 1H NMR (400 MHz, CDC13, 25 °C, TMS): δ (ppm) 8.22-8.19 (2H), 7.63-7.61 (1H), 7.52-7.48 (2H), 3.92-3.91 (2H), 3.17-3.15 (2H), 2.91-2.81 (6H), 2.15-2.10 (4H) 1.73-1.70 (1H), 0.83-0.81 (6H); LC-MS (m / z) (M+): 378.25.

[0204] (ID21) Chemical name: 1-benzoyloxy-2-naphthoic acid n-butyl ester

[0205] ID21 was prepared by the same method as ID15, except that 5,6,7,8-tetrahydro-1- hydroxy-2-naphthoic acid was replaced by 1-hydroxy-2-naphthoic acid.

[0206] 1H NMR (400 MHz, CDC13, 25 °C, TMS): δ (ppm) 8.41-8.39 (2H), 8.09-8.06 (1H), 7.91-7.82 (3H), 7.78-7.62 (3H), 7.59-7.54 (2H), 4.19-4.18 (2H), 1.41-1.37 (2H), 1.27-1.21 (2H), 0.77-0.74 (3H); LC-MS (m / z) (M+): 348.26.

[0207] (ID22) Chemical name: 1-benzoyloxy-4-tert-butyl-2-naphthoic acid n-butyl ester ID22 was prepared by the same method as ID15, except that 5,6,7,8-tetrahydro-1-hydroxy-2- naphthoic acid was replaced by 1-hydroxy-4-tert-butyl-2-naphthoic acid.

[0208] 1H NMR (400 MHz, CDC13, 25 °C, 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), 4.19-4.18 (2H), 1.73-1.70 (1H), 0.83-0.81 (15H); LC-MS (m / z) (M+): 404.51.

[0209] (C5) DNBP, chemical name: di-n-butyl phthalate;

[0210] (C6) Chemical name: 1 -benzoyloxy-2-n-butyl benzoate from CN 1257920C;

[0211] (C7) Chemical name: 3-methyl-5-tert-butyl-1,2-dibenzoyloxybenzene from WO2010078485A1.

[0212] Catalyst component preparation example B1

[0213] In a 250 ml nitrogen-purged reactor with stirring and filtration function, 2.2 g of diethoxy magnesium and 50 ml of chlorobenzene were added, then 100 ml of titanium tetrachloride / chlorobenzene solution (volume ratio 1 :1 ) was added dropwise at room temperature, then slowly heated to 90°C, 1.5 g of ID15 was added, then heated to 110°C and kept for 1 hour, then the liquid was filtered clean, the liquid was filtered off, then 100 ml of titanium tetrachloride / chlorobenzene solution (volume ratio 1 :1 ) was added again, reacted at 110°C for 1 hour, the liquid was filtered clean, 100 ml of n-heptane was added to wash the solid, repeated three times, the liquid was filtered off and dried, and the solid powder was the prepared catalyst component 15#. The titanium content, internal electron donor content and polymerization data of catalyst component 15# are shown in Table 2 below.

[0214] Catalyst component preparation examples B2-B8

[0215] The difference from catalyst component preparation example B1 is that the internal electron donor ID15 is replaced by ID16-ID22 accordingly, and the addition of titanium tetrachloride is adjusted accordingly. The titanium content, internal electron donor content and polymerization data of the prepared catalyst components 16#-22# are shown in Table 2 below.

[0216] Catalyst component preparation comparative examples B1 -B3

[0217] The difference from catalyst component preparation example B1 is that the internal electron donor ID15 is replaced by C5-C7 accordingly, and the addition of titanium tetrachloride is adjusted accordingly. The titanium content, internal electron donor content and polymerization data of the prepared catalyst components C5#-C7# are shown in Table 2 below.

[0218] Polymerization example c1 :

[0219] Propylene polymerization was carried out on a laboratory 1 5L stainless steel polymerization kettle:

[0220] Step one, first purging the reactor with refined nitrogen (its water content <1 ppm, oxygen content <1 ppm); then adding 2.2 L of liquid propylene and a set amount of hydrogen at room temperature, heating to 70°C;

[0221] Step two, before the temperature of the reactor reaches 70°C, 2.0 mL of 0.5M alkyl aluminum heptane solution, 0.4 mL of 0.5M D-donor hexane solution and 6.0 mg of the above catalyst component 15# are pre-complexed for 5 min, and then the mixture is injected into the reactor to start the reaction when the reactor reaches 70°C;

[0222] Step three, after 60 min of reaction, the material is discharged, cooled, and the reaction is stopped. The polypropylene resin is taken out and vacuum dried at 30°C for 2 h, and the obtained polypropylene product is tested for melt flow rate MFR, xylene solubles XS, GPC, etc. The specific hydrogen addition amount and test results are shown in Table 2 below.

[0223] Polymerization example d1:

[0224] The difference from polymerization example c1 is that the hydrogen addition amount is different. The specific hydrogen addition amount and test results are shown in Table 2 below.

[0225] Polymerization examples c2-c8:

[0226] The difference from polymerization example c1 is that the catalyst component 15# is replaced by catalyst components 16#-22# respectively. The specific test results are shown in Table 2 below.

[0227] Polymerization examples d2-d8:

[0228] The difference from polymerization example d1 is that the catalyst component 15# is replaced by catalyst components 16#-22# respectively. The specific test results are shown in Table 2 below.

[0229] Polymerization comparative examples c1-c3:

[0230] The difference from polymerization example c1 is that the catalyst component 15# is replaced by catalyst components C5#-C7# respectively. The specific test results are shown in Table 2 below.

[0231] Polymerization comparative examples d1-d3:

[0232] The difference from polymerization example d1 is that the catalyst component 15# is replaced by catalyst components C5#-C7# respectively. The specific test results are shown in Table 2 below.

[0233] Table 2

[0234] The polymerization results in Table 2 show that using a 3-4 cyclic modified salicylic acid derivative as an internal electron donor catalyst for propylene polymerization exhibits excellent activity and low xylene solubility. Under the same preparation process, the activity and isotacticity of the 3-4 cyclic modified salicylic acid derivative as an internal electron donor catalyst are significantly better than those of the uncyclic derivatized salicylic acid. The molecular weight distribution of the resulting polypropylene is significantly wider than that of polypropylene obtained with phthalate catalysts. Furthermore, the isotacticity is higher when R3 is 3-4 cyclic, and even higher when there is a substituent at the 5-position. The isotacticity can be further improved when there is a 5-6 cyclic ring.

[0235] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the spirit of the invention.

Claims

1. An internal electron donor compound for use as a catalyst in olefin polymerization, said internal electron donor compound having the following structure: In the formula, R0 is C or D; wherein, C is selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight chain alkyl or branched alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from heterocyclic aryl substituent; D is a substituted or unsubstituted alkyl containing 4-30 carbon atoms and at least two rings, a heteroatom-substituted heteroaryl containing at least two rings, an amino group containing at least two rings; 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; A and B are the same or different, each independently selected from ester group, amino group, amide group, sulfonyl ester group and sulfonyl amide group; wherein the substituent for substitution is aryl, halogen or heteroatom; the heteroatom is selected from N, O, S, P, Si; wherein R0 is C, R1 and R2 are bonded to each other to form a ring, and A is an ester group connected to the benzene ring of the same nucleus through a hydroxyl group, and B is an ester group connected to the benzene ring of the same nucleus through a carboxyl group.

2. The internal electron donor compound according to claim 1, characterized in that, The internal electron donor compound has the following formula I: In the formula I, G contains 4-30 carbon atoms and is a substituted or unsubstituted alkyl containing at least two rings, a heteroatom-substituted heteroaryl containing at least two rings, an amino group containing at least two rings; 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; A and B are the same or different, each independently selected from ester group, amino group, amide group, sulfonyl ester group and sulfonyl amide group; wherein the substituent for substitution is aryl, halogen or heteroatom; the heteroatom is selected from N, O, S, P, Si.

3. The internal electron donor compound according to claim 2, characterized in that, said ester group is selected from the group consisting of R4COO-, R5OOC- and R6R7NCOO-; said amino group is selected from the group consisting of R6R7N-; said amido group is selected from the group consisting of R8CONR9- and R 10 R 11 NCO-; said sulfonyl ester group is selected from the group consisting of R 12 SO3-; said sulfonyl amide group is selected from the group consisting of R 11 SO2R 13 N-; wherein R4-R 13 are the same or different, each independently selected from the group consisting of H, halogen, C2-C18 alkenyl, C1-C18 substituted or unsubstituted linear or branched alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl.

4. The internal electron donor compound according to claim 3, characterized in that, The structure of G in the formula I is adamantyl, norbornyl, N,N-dicyclopentylamino or carbazyl.

5. The internal electron donor compound according to claim 4, characterized in that, The internal electron donor compound is selected from the following compounds:

6. The internal electron donor compound according to claim 1, characterized in that, The internal electron donor compound has the following formula II: In the formula II, Ra-Re are the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight chain alkyl or branched alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom-substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from heterocyclic aryl substituent; Two or more of Ra-Re are bonded to each other to form a ring or an unsaturated bond; m and n are each an integer from 0 to 8.

7. The internal electron donor compound according to claim 6, characterized in that The internal electron donor compound has the following structure of formula II-1: In the formula II-1, R1-R 12 the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from a heterocyclic aryl substituent; Two or more of R1-R8 are bonded to each other to form a ring or an unsaturated bond.

8. The internal electron donor compound according to claim 6, characterized in that, The internal electron donor compound has the following formula II-2: In the formula II-2, R1-R 12 the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from a heterocyclic aryl substituent; R1-R 10 two or more of R1-R8are linked to each other or to the rest of the molecule to form a ring or an unsaturated bond.

9. The internal electron donor compound according to claim 6, characterized in that, The internal electron donor compound has the following formula II-3: In the formula II-3, R1-R 12 the same or different, each independently selected from H, halogen, cyano, saturated or unsaturated C1-C10 straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or heteroatom substituted alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, wherein the heteroatom is selected from N, O, S, P, Si; or is selected from a heterocyclic aryl substituent; Two or more of R1-R6 are bonded to each other to form a ring or an unsaturated bond.

10. The internal electron donor compound according to claim 6, characterized in that, The internal electron donor compound is selected from the following compounds:

11. A catalyst component for the polymerization of olefins, characterized by the fact that it comprises a solid catalyst component according to any one of the preceding claims and a cocatalyst. The catalyst component comprises a titanium compound, a magnesium compound and the internal electron donor compound according to any one of claims 1-10.

12. The catalyst component of claim 11, characterized in that, The catalyst component is prepared by contacting the magnesium compound, the titanium compound and the internal electron donor compound to obtain the catalyst component; The magnesium compound is magnesium halide or diethoxy magnesium; the titanium compound is TiXn(OR)4-n, wherein R is a hydrocarbon group with 1-20 carbon atoms, X is halogen, and n=1-4; preferably titanium tetrachloride.

13. The catalyst component of claim 12, characterized in that, The catalyst component is prepared as follows: In a nitrogen-purged reactor with stirring and filtration function, 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℃, 1-2 parts by weight of the internal electron donor compound is added, and then heated to 100-120℃ for 0.5-2 hours, then solid-liquid separation is performed, then 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added again, and then heated to 100-120℃ for 0.5-2 hours, then solid-liquid separation is performed again, then 120-160 parts by weight of titanium tetrachloride / chlorobenzene solution is added again and heated to 100-120℃ for 15-45min, then solid-liquid separation is performed, 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).

14. A method for olefin polymerization, the method comprising polymerizing olefin monomers in the presence of a catalyst obtained by reacting an organoaluminum compound, a siloxane compound and the catalyst component according to any one of claims 11-13 to form a polymer. Preferably, the olefin is propylene, and the method comprises: Step one: replace the reaction kettle with nitrogen, then sequentially add liquid propylene and hydrogen at room temperature, and heat to the set temperature; Step two: mix and react the heptane solution of the organoaluminum compound, the hexane solution of the siloxane compound as the external electron donor and the catalyst component according to any one of claims 6-8 as the catalyst, then inject the mixture into the reaction kettle when the reaction kettle reaches the set temperature to start the reaction to obtain the polymer; The set temperature is 65-75℃. The amount ratio of the catalyst component, the organoaluminum compound and the siloxane compound is 1:(5-200):(5-50).

15. The method of claim 14, wherein, The organoaluminum compound is a trialkylaluminum compound, preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trioctylaluminum or methylaluminoxane; The siloxane compound as the external electron donor is dicyclopentyl dimethoxysilane, cyclohexyl methyl dimethoxysilane or dimethoxydiphenylsilane; preferably, the siloxane compound is dicyclopentyl dimethoxysilane.

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